WO2017057758A1 - Additive for imparting low heat build-up to rubber component - Google Patents
Additive for imparting low heat build-up to rubber component Download PDFInfo
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- WO2017057758A1 WO2017057758A1 PCT/JP2016/079170 JP2016079170W WO2017057758A1 WO 2017057758 A1 WO2017057758 A1 WO 2017057758A1 JP 2016079170 W JP2016079170 W JP 2016079170W WO 2017057758 A1 WO2017057758 A1 WO 2017057758A1
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- tetrazine
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- 0 *CCc1nnc(*)nn1 Chemical compound *CCc1nnc(*)nn1 0.000 description 2
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0041—Compositions of the carcass layers
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
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- C07D257/08—Six-membered rings
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C08K3/06—Sulfur
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08L7/00—Compositions of natural rubber
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
- B60C2001/0058—Compositions of the bead apexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C2001/0066—Compositions of the belt layers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to an additive for imparting a low exothermic property to a rubber component.
- a rubber composition having low heat generation examples include (1) a rubber composition containing a functionalized polymer with enhanced affinity for carbon black and silica as fillers (Patent Document 1); ) Rubber composition containing diene elastomer, inorganic filler as reinforcing filler, polysulfated alkoxysilane as coupling agent, 1,2-dihydropyridine, and guanidine derivative (Patent Document 2); (3) Rubber component, aminopyridine derivative And a rubber composition containing an inorganic filler (Patent Document 3); (4) a rubber composition containing a terminal-modified polymer and an inorganic filler (Patent Documents 4 and 5).
- Patent Document 1 Rubber composition containing diene elastomer, inorganic filler as reinforcing filler, polysulfated alkoxysilane as coupling agent, 1,2-dihydropyridine, and guanidine derivative
- Patent Document 3 Rubber component, aminopyridine derivative And a rubber composition containing an inorgan
- the exothermic property of the rubber composition can be lowered by increasing the affinity between the filler and the rubber component. As a result, hysteresis loss (rolling) is achieved. A tire having low resistance can be obtained.
- JP 2003-514079 A Special table 2003-523472 gazette JP 2013-108004 A JP 2000-169631 A JP 2005-220323 A
- An object of the present invention is to provide an additive for imparting a low exothermic property to a rubber component.
- Another object of the present invention is to provide a rubber composition that can exhibit low heat build-up.
- Another object of the present invention is to provide a modified polymer capable of imparting low exothermic properties.
- Another object of the present invention is to provide a tire excellent in low heat generation.
- the present invention provides the following additive, modified polymer, rubber composition, method for producing the rubber composition, and tire for imparting low exothermic properties to the rubber component.
- Item 1 An additive for imparting low heat build-up to the rubber component, The following general formula (1):
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
- the additive according to Item 2 wherein the heterocyclic group is a 2-pyridyl group or a 3-pyridyl group.
- Item 5. The additive according to any one of Items 1 to 4, wherein the rubber component is a diene rubber.
- Item 6. A modified polymer produced using a rubber mixture comprising a rubber component and the additive according to any one of Items 1 to 5.
- Item 7. Item 7.
- Item 8. Item 6. A modified polymer obtained by treating a diene rubber with the additive according to any one of Items 1 to 5.
- Item 9. Item 6.
- Item 10. A modified polymer obtained by treating a diene rubber with the additive according to any one of Items 1 to 5.
- Item 10 The modified polymer according to any one of Items 7 to 9, wherein the diene rubber is natural rubber and / or synthetic diene rubber.
- Synthetic diene rubber is styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene-diene terpolymer rubber, styrene-isoprene-styrene terpolymer rubber.
- the modified polymer according to Item 10 which is at least one selected from the group consisting of styrene-butadiene-styrene terpolymer rubber.
- Item 12. Item 11.
- the modified polymer according to Item 10 wherein the diene rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.
- Item 13 Item 13.
- the modified polymer according to any one of Items 11 to 13, wherein 75 to 100 parts by mass of at least one selected from the group consisting of styrene-butadiene copolymer rubber and butadiene rubber is contained in 100 parts by mass of the rubber component.
- Item 15 A modified polymer having at least one selected from compound structures represented by the following formulas (2) to (12).
- Item 16 A rubber composition comprising a rubber component, the additive according to any one of Items 1 to 5, and an inorganic filler and / or carbon black. Item 17. Item 16. A rubber composition comprising the modified polymer according to any one of Items 6 to 15, and an inorganic filler and / or carbon black. Item 18. Item 18. The rubber composition according to Item 16 or 17, comprising 0.1 to 10 parts by mass of the additive according to any one of Items 1 to 5 with respect to 100 parts by mass of the rubber component. Item 19. Item 19.
- Item 20. The rubber composition according to Item 20.
- Item 21. Item 20.
- Item 22. The rubber composition according to any one of Items 16 to 21, wherein the rubber component is a diene rubber.
- Item 23. The rubber composition according to Item 22, wherein the diene rubber is natural rubber and / or synthetic diene rubber.
- Synthetic diene rubber is styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene-diene terpolymer rubber, styrene-isoprene-styrene terpolymer rubber.
- Item 24 The rubber composition according to Item 23, which is at least one selected from the group consisting of styrene-butadiene-styrene terpolymer rubber.
- Item 28. The additive according to any one of Items 1 to 5, wherein 50 to 100 parts by mass of styrene-butadiene copolymer rubber and / or butadiene rubber, 20 to 120 parts by mass of silica, and 1 to 5 of 100 parts by mass of the rubber component.
- Item 30. The rubber composition according to any one of Items 16 to 29, which is used for a tread member.
- Item 30. A tire produced using the rubber composition according to any one of Items 16 to 29.
- Item 34. Step (A) of mixing a rubber component, an additive according to any one of Items 1 to 5, and a raw material component containing an inorganic filler and / or carbon black, and a mixture obtained in Step (A), and The manufacturing method of a rubber composition including the process (B) which mixes a vulcanizing agent.
- Step (A) is a step of mixing the rubber component and the additive according to any one of Items 1 to 5 (A-1), the mixture obtained in Step (A-1), and inorganic filling Item 35.
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
- a low exothermic agent comprising a tetrazine compound represented by the formula: Item 38.
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
- An antipyretic agent comprising a tetrazine compound represented by the formula: Item 39.
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
- the present invention can provide an additive for imparting low exothermic properties to the rubber component.
- the additive contains a tetrazine compound, and the additive disperses the inorganic filler and / or carbon black in the rubber component.
- the present invention can provide a rubber composition that can exhibit low heat build-up and a modified polymer that can impart low heat build-up.
- the present invention provides a fuel-efficient tire by producing a tire using a rubber composition that can exhibit low heat build-up, thereby reducing the rolling resistance of the tire and lowering the heat build-up of the tire. can do.
- a rubber composition highly filled with silica exhibits high low heat build-up, a low fuel consumption tire having high exercise performance can be provided.
- FIG. 3 is a 13 C-NMR chart of a tetrazine compound (1b). It is a 13 C-NMR chart of S-SBR.
- FIG. 3 is an enlarged view of FIG. 2.
- 3 is a 13 C-NMR chart of modified S-SBR modified with a tetrazine compound (1b).
- FIG. 5 is an enlarged view of FIG. 4.
- FIG. 6 is a diagram comparing 13 C-NMR charts of a tetrazine compound (1b), S-SBR, and modified S-SBR.
- additive of the present invention is represented by the following general formula ( 1) or a salt thereof (hereinafter sometimes referred to as “tetrazine compound (1)”).
- X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
- alkyl group is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group, and specifically includes, for example, methyl, ethyl, n-propyl, isopropyl , N-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl group, etc.
- linear or branched alkyl groups ; cyclic alkyl groups having 3 to 8 carbon atoms (particularly 3 to 6 carbon atoms) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
- the preferred alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or n-pentyl group. Particularly preferred is a methyl or ethyl group.
- alkylthio group is not particularly limited and includes, for example, a linear, branched or cyclic alkylthio group, and specifically includes, for example, methylthio, ethylthio, n-propylthio, isopropyl 1 carbon number such as thio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, 1-ethylpropylthio, n-pentylthio, neopentylthio, n-hexylthio, isohexylthio, 3-methylpentylthio group Straight chain or branched alkylthio group having 6 to 6 carbon atoms (particularly 1 to 4 carbon atoms); 3 to 8 carbon atoms such as cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,
- alkylthio groups include a cyclic alkylthio group (particularly having 3 to 6 carbon atoms).
- Preferred alkylthio groups are methylthio, ethylthio, isopropylthio, or isobutylthio groups, and more preferred are methylthio groups or ethylthio groups.
- the “aralkyl group” is not particularly limited, and examples thereof include benzyl, phenethyl, trityl, 1-naphthylmethyl, 2- (1-naphthyl) ethyl, 2- (2-naphthyl) ethyl group and the like. Can be mentioned.
- a more preferred aralkyl group is a benzyl group or a phenethyl group, more preferably a benzyl group.
- aryl group is not particularly limited, and examples thereof include phenyl, biphenyl, naphthyl, dihydroindenyl, 9H-fluorenyl group and the like.
- a more preferred aryl group is a phenyl group or a naphthyl group, and more preferably a phenyl group.
- arylthio group is not particularly limited, and examples thereof include phenylthio, biphenylthio, naphthylthio groups and the like.
- the “heterocyclic group” is not particularly limited, and examples thereof include 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3-pyrimidyl, Pyridazyl, 4-pyridazyl, 4- (1,2,3-triazyl), 5- (1,2,3-triazyl), 2- (1,3,5-triazyl), 3- (1,2,4 -Triazyl), 5- (1,2,4-triazyl), 6- (1,2,4-triazyl), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7- Quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl
- the “amino group” includes not only an amino group represented by —NH 2 but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s 1 to 6 carbon atoms (particularly carbon number) such as -butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group, etc.
- linear or branched monoalkylamino group linear or branched alkyl having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms) such as dimethylamino, ethylmethylamino, diethylamino group, etc.
- substituted amino groups such as dialkylamino groups having two groups.
- alkyl group, alkylthio group, aralkyl group, aryl group, arylthio group, heterocyclic group and amino group each may have one or more substituents.
- the “substituent” is not particularly limited, and examples thereof include halogen atoms, amino groups, aminoalkyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, carboxyalkyl groups, formyl groups, and nitrile groups.
- the substituent may preferably have 1 to 5, more preferably 1 to 3.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable.
- aminoalkyl group is not particularly limited, and examples thereof include aminoalkyl groups such as aminomethyl, 2-aminoethyl, and 3-aminopropyl groups.
- alkoxycarbonyl group is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
- acyl group is not particularly limited, and examples thereof include linear or branched alkylcarbonyl groups having 1 to 4 carbon atoms such as acetyl, propionyl, and pivaloyl groups.
- acyloxy group is not particularly limited, and examples thereof include acetyloxy, propionyloxy, n-butyryloxy group and the like.
- amide group is not particularly limited, and examples thereof include carboxylic acid amide groups such as acetamide and benzamide groups; thioamide groups such as thioacetamide and thiobenzamide groups; N-methylacetamide and N-benzylacetamide. N-substituted amide groups such as a group;
- the “carboxyalkyl group” is not particularly limited, and examples thereof include carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl, carboxy-n-butyl, and carboxy-n-hexyl groups. And a carboxy-alkyl group (preferably an alkyl group having 1 to 6 carbon atoms having a carboxy group).
- hydroxyalkyl group is not particularly limited, and examples thereof include hydroxy-alkyl groups such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl groups (preferably hydroxy groups). And an alkyl group having 1 to 6 carbon atoms).
- the “alkoxy group” is not particularly limited and includes, for example, a linear, branched or cyclic alkoxy group, and specifically includes, for example, methoxy, ethoxy, n-propoxy, iso
- aryloxy group is not particularly limited, and examples thereof include phenoxy, biphenyloxy, naphthoxy group and the like.
- the “salt” of the tetrazine compound represented by the general formula (1) is not particularly limited, and includes all kinds of salts.
- examples of such salts include inorganic acid salts such as hydrochlorides, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates; alkali metal salts such as sodium salts and potassium salts; magnesium salts and calcium Examples include alkaline earth metal salts such as salts; quaternary ammonium salts such as dimethylammonium and triethylammonium.
- preferred compounds are those in which X 1 and X 2 are the same or different and may have a substituent, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. It is a compound which is an aryl group which may have a group, or a heterocyclic group which may have a substituent.
- X 1 and X 2 are the same or different and have an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a compound that is an optionally substituted heterocyclic group.
- tetrazine compound (1) is that X 1 and X 2 are the same or different and have a benzyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent.
- An optionally substituted 2-pyridyl group, an optionally substituted 3-pyridyl group, an optionally substituted 4-pyridyl group, and an optionally substituted 2-furanyl group An optionally substituted thienyl group, an optionally substituted 1-pyrazolyl group, an optionally substituted 2-pyrimidyl group, or an optionally substituted substituent
- a compound that is a good 2-pyrazyl group Among these, a 2-pyridyl group that may have a substituent, a 3-pyridyl group that may have a substituent, or a substituent. Particularly preferred are compounds which may be 2-furanyl groups.
- tetrazine compound (1) for example, 1,2,4,5-tetrazine, 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine, 3,6-diphenyl-1,2,4,5-tetrazine, 3,6-dibenzyl-1,2,4,5-tetrazine, 3,6-bis (2-furanyl) -1,2,4,5-tetrazine, 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine, 3,6-bis (2-thienyl) -1,2,4,5-tetrazine, 3-methyl-6- (2-pyridyl) -1,2,4,5-tete
- preferred tetrazine compounds (1) are 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine and 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine.
- more preferred tetrazine compound (1) is 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, And 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine.
- the tetrazine compound (1) By adding the tetrazine compound (1) to the rubber component, low exothermic property can be imparted to the rubber component. Since the tire produced (manufactured) from such a rubber composition containing the tetrazine compound (1) can impart low heat build-up, rolling resistance is reduced, and as a result, low fuel consumption performance is exhibited.
- the rubber component is not particularly limited.
- natural rubber NR
- synthetic diene rubber a mixture of natural rubber and synthetic diene rubber, and other non-diene rubbers Is mentioned.
- natural rubber examples include natural rubber latex, technically rated rubber (TSR), smoked sheet (RSS), gutta percha, Tochu-derived natural rubber, guayule-derived natural rubber, and Russian dandelion-derived natural rubber.
- Modified natural rubbers such as modified epoxidized natural rubber, methacrylic acid-modified natural rubber, and styrene-modified natural rubber are also included in the natural rubber of the present invention.
- Synthetic diene rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene ternary copolymer Examples thereof include polymer rubber (EPDM), styrene-isoprene-styrene ternary block copolymer (SIS), styrene-butadiene-styrene ternary block copolymer (SBS), and modified synthetic diene rubbers thereof.
- the modified synthetic diene rubber includes a diene rubber by a modification technique such as main chain modification, one terminal modification, or both terminal modification.
- examples of the modified functional group of the modified synthetic diene rubber include various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group, and one or more of these functional groups are modified synthetic diene series. It may be contained in rubber.
- the method for producing the synthetic diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Further, there is no particular limitation on the glass transition point of the synthetic diene rubber.
- the ratio of cis / trans / vinyl in the double bond portion of natural rubber and synthetic diene rubber is not particularly limited, and any ratio can be preferably used.
- the number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but a number average molecular weight of 500 to 3000000 and a molecular weight distribution of 1.5 to 15 are preferable.
- non-diene rubber known rubbers can be widely used.
- the rubber component can be used alone or in combination (blend) of two or more.
- preferable rubber components are natural rubber, IR, SBR, BR or a mixture of two or more selected from these, more preferably natural rubber, SBR, BR or a mixture of two or more selected from these.
- the blend ratio is not particularly limited, but it is preferable to blend SBR, BR or a mixture thereof in a ratio of 50 to 100 parts by mass in 100 parts by mass of the rubber component, and 75 to 100 parts by mass. It is particularly preferable to blend.
- the total amount of SBR and BR is preferably in the above range. In this case, SBR is 50 to 100 parts by mass, and BR is preferably in the range of 0 to 50 parts by mass.
- Modified Polymer The modified polymer of the present invention is produced using a rubber mixture containing a diene rubber and the additive of the present invention.
- the modified polymer of the present invention is a modified polymer obtained by treating a diene rubber with the tetrazine compound (1).
- tetrazine compound (1) can be further modified by allowing the tetrazine compound (1) to act on a diene rubber modified with an epoxy group, amino group, alkoxysilyl group, hydroxyl group or the like.
- the raw material for producing the modified polymer of the present invention contains the tetrazine compound (1) and a diene rubber.
- the amount of the tetrazine compound (1) is not particularly limited. For example, it is usually 0.1 to 10 parts by mass, preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition described later. What is necessary is just to adjust suitably so that it may be 5 mass parts, More preferably, it is 0.5-2 mass parts.
- the modified polymer of the present invention has a heteroatom such as a nitrogen atom, and since this heteroatom interacts strongly with silica and carbon black, the dispersibility of silica or carbon black in the diene rubber component is improved. It is possible to impart high low heat build-up to the modified polymer.
- the modified polymer of the present invention preferably has at least one selected from compound structures represented by the following formulas (2) to (12).
- R represents a halogen atom or an alkyl group.
- modified polymer of the present invention is considered to be obtained by the following reaction mechanism.
- a reverse electron request type Aza-Diels-Alder reaction proceeds between the tetrazine compound (1) and the double bond in the rubber component.
- reaction Formula-1 As the reactions shown in the following reaction formulas -1 to 4 proceed, the tetrazine compound (1) is bonded to the double bond site of the diene rubber to form a six-membered ring structure, A modified polymer is produced.
- reaction formula-1 the reverse electron request type Aza-Diels-Alder reaction between the double bond site of the diene rubber represented by the formula (A-1) and the tetrazine compound (1) results in the formula (B-1
- the bicyclo ring structure represented by this is formed.
- the —N ⁇ N— moiety in this bicyclo ring structure is easily denitrogenated, and has a six-membered ring structure represented by the formula (C-1), (C-2) or (C-3).
- a modified polymer is formed which has a six-membered ring structure represented by formula (2) by being further oxidized by oxygen in the air.
- reaction formula-2 as in the reaction formula-1, the double bond site of the diene rubber represented by the formula (A-2) and the tetrazine compound (1) are used to formula (B-2) or ( B-2 ′) and then a six-membered ring structure represented by formulas (C-4) to (C-9), and then represented by formula (3) or (4) A modified polymer having a six-membered ring structure is produced.
- Reaction formula-3 the double bond site of the diene rubber represented by the formula (A-2) and the tetrazine compound (1) are used to formula (B-2) or ( B-2 ′) and then a six-membered ring structure represented by formulas (C-4) to (C-9), and then represented by formula (3) or (4) A modified polymer having a six-membered ring structure is produced.
- reaction formula-3 a reverse electron request type Aza-Diels-Alder reaction between the double bond site of the diene rubber represented by the formula (A-3) and the tetrazine compound (1) results in the formula (B-3 ) Or (B-3 ′), a modified polymer having a six-membered ring structure represented by formulas (5) to (8) is produced by denitrogenation.
- R on the double bond site of the diene rubber represented by the formula (A-3) is a halogen atom
- a modified polymer having a six-membered ring structure represented by (2) is produced.
- reaction formula-4 as in the reaction of the reaction formula-3, the reaction of the double bond site of the diene rubber represented by the formula (A-4) with the tetrazine compound (1) results in the reaction of the formula (B- 4) Or, after forming a bicyclo ring structure represented by (B-4 ′), a modified polymer having a six-membered ring structure represented by formulas (9) to (12) is produced.
- silica can be dispersed in the rubber component by the action of the additive of the present invention.
- the silica dispersion mechanism is presumed as follows.
- the modified polymer produced by the reaction of the rubber component and the tetrazine compound (1) with the nitrogen atom of the tetrazine compound (1) constituting the additive of the present invention has high affinity with silica. It is presumed that the affinity for silica is further improved by the presence of nitrogen atoms. In particular, the affinity with silica is enhanced by introducing a substituent or a polar group having a hetero atom into the 3-position (X 1 group) and the 6-position (X 2 group) of the tetrazine compound (1). Is guessed. Therefore, it is considered that silica is dispersed in the rubber component by the additive of the present invention.
- the method for producing a modified polymer of the production method the present invention modified polymers is not particularly limited.
- the modified polymer of the present invention is produced using, for example, a rubber mixture containing at least one rubber component selected from the group consisting of natural rubber and synthetic diene rubber and a tetrazine compound (1).
- the rubber component when the rubber component is solid, the rubber component and the tetrazine compound (1) are kneaded under heating conditions (kneading method);
- the rubber component is liquid (liquid)
- a method of mixing the rubber component solution or emulsion (suspension) and the tetrazine compound (1) under heating conditions (liquid mixing method) and the like can be mentioned.
- the heating temperature is not particularly limited.
- the upper limit of the temperature of the rubber composition is preferably 80 to 190 ° C., more preferably 90 to 160 ° C., 100 More preferably, it is ⁇ 150 ° C.
- the upper limit of the temperature of the liquid rubber composition is preferably 80 to 190 ° C, more preferably 90 to 160 ° C, and further preferably 100 to 150 ° C.
- the mixing time or kneading time is not particularly limited.
- the kneading method it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 60 seconds to 7 minutes. More preferably it is.
- the time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 40 minutes, and further preferably 60 seconds to 30 minutes.
- the blending amount of the tetrazine compound (1) is not particularly limited.
- it is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition.
- the content is 0.25 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass.
- Rubber composition contains a rubber component, the additive of the present invention, and an inorganic filler and / or carbon black.
- the rubber composition of the present invention contains the modified polymer, an inorganic filler and / or carbon black.
- the rubber component, the additive of the present invention, and the modified polymer are as described above.
- the amount of the additive of the present invention is usually 0.1 to 10 parts by weight, preferably 0.25 to 5 parts by weight, more preferably 100 parts by weight of the rubber component in the rubber composition. Is 0.5 to 2 parts by mass.
- the blending amount of the inorganic filler and / or carbon black is not particularly limited. For example, it is usually 2 to 200 parts by weight, preferably 30 to 130 parts by weight, more preferably 100 parts by weight of the rubber component. Is 35 to 110 parts by mass. When both inorganic filler and carbon black are blended, the total amount of both components may be adjusted as appropriate within the above range.
- the blending amount of the inorganic filler and / or carbon black is 2 parts by mass or more, it is preferable from the viewpoint of improving the reinforcing property of the rubber composition, and if it is 200 parts by mass or less, it is preferable from the viewpoint of reducing rolling resistance.
- the above-mentioned inorganic filler or carbon black is usually used for improving the reinforcing property of rubber.
- carbon black is not included in the inorganic filler.
- the inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry.
- examples of inorganic compounds that can be used include silica; alumina such as ⁇ -alumina and ⁇ -alumina (Al 2 O 3 ); alumina monohydrate such as boehmite and diaspore (Al 2 O 3 .H 2 O); gibbsite Aluminum hydroxide [Al (OH) 3 ], such as bayerite; aluminum carbonate [Al 2 (CO 3 ) 2 ], magnesium hydroxide [Mg (OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), Talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), titanium white (TiO 2 ), titanium black (TiO 2n-1 ), calcium oxide (CaO), hydroxylated Calcium [Ca (OH) 2 ], aluminum magnesium oxide (MgO
- the compounding amount of the inorganic filler is usually 10 to 200 parts by mass with respect to 100 parts by mass of the rubber component.
- silica is preferable from the viewpoint of imparting rubber strength, more preferably silica alone, or silica and one or more inorganic compounds usually used in the rubber industry can be used in combination.
- the inorganic compound other than silica and silica is used in combination as the inorganic filler, it may be appropriately adjusted so that the total amount of all components of the inorganic filler is within the above range.
- Silica is preferably added because it can impart rubber strength. Any commercially available silica can be used. Among these, preferable silica is wet silica, dry silica, or colloidal silica, and more preferably wet silica. These silicas may be subjected to organic treatment on the surface of the silica in order to improve the affinity with the rubber component.
- the BET specific surface area of silica is not particularly limited, and examples thereof include a range of 40 to 350 m 2 / g. Silica having a BET specific surface area within this range has an advantage that both rubber reinforcement and dispersibility in the rubber component can be achieved.
- the BET specific surface area is measured according to ISO 5794/1.
- silica having a BET specific surface area in the range of 80 to 300 m 2 / g, more preferably silica having a BET specific surface area of 100 to 270 m 2 / g, particularly preferably.
- the compounding amount of silica is usually 20 to 120 parts by mass, preferably 30 to 100 parts by mass, and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component.
- the exercise performance is improved by adding silica, but the low exothermic property tends to be deteriorated by adding a large amount.
- excellent low heat build-up is expressed even when a large amount of silica is blended.
- the amount of silica blended when achieving both athletic performance and low fuel consumption performance is usually 40 to 120 parts by weight, preferably 60 to 115 parts by weight, more preferably 100 parts by weight of the rubber component.
- the amount is preferably 70 to 110 parts by mass.
- the additive of the present invention can be used as an inorganic filler and / or a carbon black dispersant, a low heat generation agent, a heat generation preventive material, or a heat generation inhibitor, and preferably a rubber dispersant or a low heat generation rubber. It can be used as an agent, an exothermic material for rubber, or an exothermic inhibitor for rubber.
- the carbon black carbon black is not particularly limited, and examples thereof include commercially available carbon black and Carbon-Silica Dual phase filler.
- carbon black By containing carbon black in the rubber component, it is possible to enjoy the effect of reducing the electrical resistance of the rubber and suppressing charging, and the effect of improving the strength of the rubber.
- carbon black for example, high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade carbon Black etc. are mentioned. Among them, preferable carbon black is SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon black.
- the DBP absorption of carbon black is not particularly limited, preferably 60 ⁇ 200cm 3 / 100g, more preferably 70 ⁇ 180cm 3 / 100g or more, particularly preferably 80 ⁇ 160cm 3 / 100g.
- the nitrogen adsorption specific surface area (measured in accordance with N2SA, JIS K 6217-2: 2001) of carbon black is preferably 30 to 200 m 2 / g, more preferably 40 to 180 m 2 / g, particularly preferably. 50 to 160 m 2 / g.
- the tetrazine compound (1) or the reaction product of the rubber component and the tetrazine compound (1) interacts strongly with carbon black. Therefore, according to the rubber composition of the present invention, the dispersibility of carbon black is greatly improved, and the low heat buildup of the rubber composition can be remarkably improved.
- the compounding amount of carbon black is usually 2 to 150 parts by mass, preferably 4 to 120 parts by mass, and more preferably 6 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount in carbon black is 2 parts by mass or more, it is preferable from the viewpoint of securing antistatic performance and rubber strength performance, and if it is 150 parts by mass or less, it is preferable from the viewpoint of reducing rolling resistance.
- the rubber composition of the present invention includes compounding agents commonly used in the rubber industry, such as anti-aging agents, ozone, and the like. Inhibitors, softeners, processing aids, waxes, resins, foaming agents, oils, stearic acid, zinc white (ZnO), vulcanization accelerators, vulcanization retarders, vulcanizing agents (sulfur), etc. It can be appropriately selected and blended within a range that does not impair the purpose. As these compounding agents, commercially available products can be suitably used.
- an agent may be blended.
- silane coupling agent that can be used in combination with the inorganic filler is not particularly limited, and a commercially available product can be suitably used.
- silane coupling agents include sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, and alkyl-based silane coupling agents.
- sulfide-based silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, and bis ( 2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (2-triethoxysilyl) Ethyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide, bis (2- Triethoxy
- thioester-based silane coupling agents include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, and 3-lauroylthiopropyltriethoxysilane.
- thiol-based silane coupling agent examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like.
- olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, allyltri Ethoxysilane, p-styryltrimethoxysilane, 3- (methoxydimethoxydimethylsilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (trimethoxysilyl) Propyl methacrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- [tris (tri Chirushirokishi) silyl
- epoxy-based silane coupling agents include 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, and triethoxy (3-glycidyloxypropyl) silane. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferred.
- amino silane coupling agents examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- Examples include 2-aminoethyl-3-aminopropyltrimethoxysilane. Of these, 3-aminopropyltriethoxysilane is preferred.
- alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxy.
- Examples include silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Of these, methyltriethoxysilane is preferred.
- bis (3-triethoxysilylpropyl) tetrasulfide can be particularly preferably used.
- one silane coupling agent may be used alone, or two or more silane coupling agents may be used in combination.
- the compounding amount of the silane coupling agent of the rubber composition of the present invention is preferably 0.1 to 20 parts by mass, particularly preferably 3 to 15 parts by mass with respect to 100 parts by mass of the inorganic filler. If it is 0.1 parts by mass or more, the effect of improving the low heat build-up of the rubber composition can be expressed more suitably, and if it is 20 parts by mass or less, the cost of the rubber composition is reduced and the economic efficiency is improved. It is because it improves.
- the use of the rubber composition of the present invention is not particularly limited, and examples thereof include tires, anti-vibration rubbers, conveyor belts, and rubber portions thereof. Among these, a preferable use is a tire.
- the production method of the rubber composition of the present invention is not particularly limited.
- the rubber composition production method of the present invention is obtained, for example, in the step (A) of kneading the rubber component, the additive of the present invention, and the raw material component containing an inorganic filler and / or carbon black, and the step (A). And a step (B) of kneading the vulcanizing agent.
- the step (A) is a step of kneading the rubber component, the additive of the present invention, and the raw material component containing the inorganic filler and / or carbon black, and means that it is a step before blending the vulcanizing agent. ing.
- step (A) the above-mentioned other compounding agents and the like can be further blended as necessary.
- Examples of the kneading method in step (A) include a method of kneading a composition containing a rubber component, an additive of the present invention, and a raw material component containing an inorganic filler and / or carbon black.
- the entire amount of each component may be kneaded at a time, or each component may be dividedly added and kneaded according to the purpose such as viscosity adjustment.
- the additive of the present invention is added and kneaded, or after the rubber component and the additive of the present invention are kneaded, the inorganic filler and Alternatively, carbon black may be added and kneaded. In order to disperse each component uniformly, the kneading operation may be repeated.
- the step (A-1) of kneading the rubber component and the additive of the present invention, and the mixture (modified polymer) obtained in the step (A-1) and A two-stage kneading method including a step (A-2) of kneading a raw material component containing an inorganic filler and / or carbon black can be mentioned.
- the temperature at which the rubber composition is mixed in the step (A) is not particularly limited.
- the upper limit of the temperature of the rubber composition is preferably 120 to 190 ° C, and preferably 130 to 175 ° C. More preferably, it is 140 to 170 ° C.
- the mixing time in step (A) is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 2 minutes to 7 minutes. preferable.
- the temperature at which the rubber component and the additive of the present invention are mixed in the step (A-1) is preferably 80 to 190 ° C, more preferably 90 to 160 ° C, and more preferably 100 to 150 ° C. More preferably. This is because when the mixing temperature is lower than 80 ° C., the reaction does not proceed, and when it is 190 ° C. or higher, the deterioration of the rubber proceeds.
- the mixing time in step (A-1) is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 60 seconds to 7 minutes. This is because when the mixing time is shorter than 10 seconds, the reaction does not proceed sufficiently, and when it is longer than 20 minutes, the productivity is lowered.
- the temperature at which the mixture (modified polymer) obtained in step (A-1) in step (A-2) is mixed with the inorganic filler and / or carbon black is not particularly limited.
- the upper limit of the temperature is preferably 120 to 190 ° C, more preferably 130 to 175 ° C, and further preferably 140 to 170 ° C.
- the mixing time in step (A-2) is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 2 minutes to 7 minutes. Is more preferable.
- the blending amount of the tetrazine compound (1) which is the additive of the present invention is not particularly limited, and is, for example, 0.1 to 10 with respect to 100 parts by mass of the rubber component, preferably It is 0.25 to 5, more preferably 0.5 to 2.
- the double bond part of the rubber component reacts with the additive of the present invention, the tetrazine compound (1), and is represented by the above formulas (2) to (12).
- a modified polymer having a ring structure is formed, and a mixture in which the inorganic filler and / or carbon black is suitably dispersed can be obtained.
- Step (B) is a step (B) in which the mixture obtained in step (A) and the vulcanizing agent are mixed, and means the final stage of kneading.
- step (B) a vulcanization accelerator or the like can be further blended as necessary.
- Process (B) can be performed under heating conditions.
- the heating temperature in this step is not particularly limited, and is preferably 60 to 140 ° C., more preferably 80 to 120 ° C., and still more preferably 90 to 120 ° C.
- the mixing (or kneading) time is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 60 seconds to 5 minutes. .
- step (B) When proceeding from step (A) to step (B), it is preferable to proceed to the next step (B) after lowering the temperature after completion of the previous step by 30 ° C. or more.
- various compounding agents such as a vulcanization accelerator such as stearic acid and zinc white, an anti-aging agent, etc., which are usually compounded in the rubber composition, are optionally added to the step (A Or in step (B).
- the rubber composition in the present invention is mixed or kneaded using a Banbury mixer, roll, intensive mixer, kneader, twin screw extruder or the like. Then, it is extruded and processed in the extrusion process, and is formed as, for example, a tread member or a sidewall member. Subsequently, it is pasted and molded by a normal method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.
- Tire The tire of the present invention is a tire produced using the additive, rubber composition or modified polymer of the present invention.
- Examples of the tire of the present invention include pneumatic tires (radial tires, bias tires, etc.), solid tires, and the like.
- tires for passenger cars there are no particular restrictions on the use of the tire, and examples include tires for passenger cars, tires for high loads, tires for motorcycles (motorcycles), studless tires, etc. Among them, they can be suitably used for tires for passenger cars.
- the shape, structure, size and material of the tire of the present invention are not particularly limited and can be appropriately selected depending on the purpose.
- the additive, the rubber composition, or the modified polymer is used in at least one member selected from a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion, and a shoulder portion.
- the tire tread portion or the sidewall portion of the pneumatic tire is formed of the rubber composition.
- the tread portion is a portion that has a tread pattern and is in direct contact with the road surface, and is the outer skin portion of the tire that protects the carcass and prevents wear and trauma, and the cap tread and / or cap tread that constitutes the ground contact portion of the tire.
- a base tread arranged inside.
- the sidewall portion is, for example, a portion from the lower side of the shoulder portion to the bead portion in the pneumatic radial tire, which protects the carcass and is the most bent portion when traveling.
- the bead area is the part that fixes both ends of the carcass cord and simultaneously fixes the tire to the rim.
- a bead is a structure in which high carbon steel is bundled.
- the belt part is a reinforcing band stretched in the circumferential direction between the radial tread and the carcass.
- the carcass is tightened like a heel and the rigidity of the tread is increased.
- the carcass portion is a portion of the cord layer that forms the skeleton of the tire, and plays a role to withstand the load, impact, and filling air pressure that the tire receives.
- the shoulder part is the shoulder part of the tire and serves to protect the carcass.
- the tire of the present invention can be manufactured according to a method known so far in the field of tires. Moreover, as gas with which a tire is filled, normal or adjusted oxygen partial pressure air; an inert gas such as nitrogen, argon, or helium can be used.
- an inert gas such as nitrogen, argon, or helium
- the tire of the present invention has low heat generation properties and the rolling resistance of the tire is reduced, the fuel consumption of the automobile can be reduced.
- a rubber composition highly filled with silica exhibits high low heat build-up, a low fuel consumption tire having high exercise performance can be provided.
- Production Example 1 Production of 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine (1a)
- 24 g (0.23 mol) of 3-cyanopyridine was added with water.
- Hydrazine (15 g, 1.3 equivalents) and methanol (48 mL) were added, and the mixture was stirred at room temperature.
- 3.6 g (15% by weight) of sulfur was added to this mixture, and a reflux tube was attached, followed by heating and stirring at an external temperature of 70 ° C. overnight.
- the reaction solution was ice-cooled, and the crystals were filtered and washed with a small amount of cold methanol.
- the crude crystals were dried under reduced pressure to obtain 19 g of orange dihydrotetrazine crude crystals.
- Production Example 2 Production of 3,6-diphenyl-1,2,4,5-tetrazine (1d) A 500 mL four-necked flask was charged with 120 g (1.16 mol) of benzonitrile and 76 g (1.3 equivalents) of hydrazine hydrate. ) And 348 mL of methanol were added and stirred at room temperature. Next, 10 g (8.6% by weight) of sulfur was added to the mixture, and a reflux tube was attached, followed by heating and stirring overnight at an external temperature of 70 ° C. The resulting reaction solution was ice-cooled, and the crystals were filtered and washed with a small amount of cold methanol.
- the obtained crude crystals were dissolved in 2.5 L of warm methanol, insoluble matters were filtered off, and then the solvent of the filtrate was distilled off.
- the obtained crude crystals were dried under reduced pressure to obtain 48 g of yellow dihydrotetrazine crude crystals.
- Production Example 3 Production of 3,6-dibenzyl-1,2,4,5-tetrazine (1e) In a 300 mL four-necked flask, 58.5 g (0.5 mol) of phenylacetonitrile and 100 g of hydrazine hydrate (4. 0 equivalents) was added and stirred at room temperature. Next, 9.0 g (15% by weight) of sulfur was added to the mixture, and a reflux tube was attached, and the mixture was heated and stirred overnight at an external temperature of 90 ° C. The reaction solution was ice-cooled, 100 mL of distilled water was added and the contents were pulverized with a shell, and the crystals were filtered and washed with distilled water. The crude crystals were dried under reduced pressure to obtain 61 g of crude crystals containing white dihydrotetrazine.
- Production Example 4 Production of 3,6-bis (2-furanyl) -1,2,4,5-tetrazine (1f) To a 50 mL three-necked flask, 3 g (0.032 mol) of 2-furonitrile and hydrazine hydrate 3 .3 g (2.0 equivalents) and 15 mL of ethanol were added, and the mixture was stirred under ice-cooling. Next, 0.3 gram (10% by weight) of sulfur was added to the mixture, and a reflux tube was attached, followed by heating and stirring at an external temperature of 80 ° C. for 2 hours. The obtained reaction solution was ice-cooled, the crystals were filtered, and dried under reduced pressure to obtain 2.48 g of yellow dihydrotetrazine crude crystals.
- Tetrazine compound (1a) 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine (compound produced in Production Example 1)
- Tetrazine compound (1b) 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, manufactured by Tokyo Chemical Industry Co., Ltd.
- Tetrazine compound (1c) 3,6-bis (4-Pyridyl) -1,2,4,5-tetrazine, manufactured by Tokyo Chemical Industry Co., Ltd.
- Tetrazine compound (1d) 3,6-diphenyl-1,2,4,5-tetrazine (Production Example 2) Compound produced in * 55: Tetrazine compound (1e): 3,6-dibenzyl-1,2,4,5-tetrazine (compound produced in Production Example 3) * 56: Tetrazine compound (1f): 3,6-bis (2-furanyl) -1,2,4,5-tetrazine (compound produced in Production Example 4) * 57: Tetrazine compound (1 g): 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine (compound produced in Production Example 5) * 58: Tetrazine compound (1h): 3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine (compound produced in Production Example 6) * 59: Tetrazine compound (1i): 3,6-bis (2-thienyl) -1,2,4,5-tetrazine (compound produced in Production Example
- Tetrazine compound (1b), S-SBR, and modified S-SBR extracted with THF were dissolved in CDCl 3 and 13 C-NMR was measured.
- the measurement results of the tetrazine compound (1b) are shown in FIG. 1, the measurement results of S-SBR are shown in FIGS. 2 and 3, and the measurement results of modified S-SBR extracted with THF are shown in FIGS. Further, FIG. 6 shows a comparison of 13 C-NMR charts of the tetrazine compound (1b), S-SBR, and modified S-SBR.
- the tetrazine compound is a compound having a red to purple color, and the color peculiar to tetrazine disappears when kneaded with SBR. Similarly, in the polymers other than SBR shown in the production example of the tetrazine-modified polymer, the color peculiar to the tetrazine compound disappears, so that the double bond of the polymer and the reverse electron request type Aza-Diels-Alder reaction are in progress. Recognize.
- Examples 1 to 129 The components described in the steps (A) of Tables 4 to 13 below were mixed in the proportions (parts by mass), and kneaded for 5 minutes with a Banbury mixer while adjusting the rotation speed so that the maximum temperature of the mixture was 160 ° C. . After curing until the temperature of the mixture reaches 80 ° C. or less, each component described in Steps (B) of Tables 4 to 11 is added in the proportion (part by mass), and the maximum temperature of the mixture becomes 110 ° C. or less.
- the rubber composition was manufactured by kneading while adjusting as described above.
- Examples 130-133 The components described in the step (A-1) in Table 14 below are mixed in the ratio (parts by mass), and the number of revolutions is adjusted so that the temperature of the mixture maintains the temperature described in Table 14 (mixture temperature) with a Banbury mixer. While kneading, the components shown in Table 14 (kneading time) were kneaded, and then each component described in step (A-2) was added at the ratio, and the temperature of the mixture was adjusted to 160 ° C. for 4 minutes. Kneaded. After curing until the temperature of the mixture reaches 80 ° C. or less, add each component described in step (B) of Table 14 at that ratio, and adjust the number of rotations so that the maximum temperature is 110 ° C. or less with a Banbury mixer. The rubber composition was manufactured by kneading for 1 minute while adjusting.
- Low exothermic index ⁇ (tan ⁇ of rubber composition not containing tetrazine compound (1)) / (tan ⁇ of rubber composition of the present invention) ⁇ ⁇ 100
- the rubber compositions of any of the examples exhibited excellent heat resistance against the comparative rubber composition to which no tetrazine compound was added.
- the rubber compositions of 131 to 133 exhibit a low exothermic index of 130 or more and less than 140, and rubbers of Examples 13, 29, 63, 68, 72, 74, 83, 85, 87, 111, 113, 119, 124 and 128
- the composition exhibited a low exothermic index of 140 or more and less than 150.
- the rubber compositions of Examples 3, 5, 19, 30, 35, 62, 66, 67, 79, 82, 99, 110, 114, 116, 117, 126, 127 and 129 have a low exothermic index of 150. The above is shown.
- the rubber composition of the present invention improves the dispersibility of the inorganic filler (for example, silica) and / or carbon black by blending the tetrazine compound (1), and is excellent in low heat generation. Even if a silane coupling agent is not added to the rubber composition, the rubber composition is excellent in low heat build-up. Therefore, it can be used as each member of various pneumatic tires of various automobiles, in particular, as a tread member, sidewall member, bead area member, belt member, carcass member, and shoulder member of a pneumatic radial tire. it can.
Abstract
Description
項1.
ゴム成分に低発熱性を付与するための添加剤であって、
下記一般式(1): That is, the present invention provides the following additive, modified polymer, rubber composition, method for producing the rubber composition, and tire for imparting low exothermic properties to the rubber component.
An additive for imparting low heat build-up to the rubber component,
The following general formula (1):
で表されるテトラジン化合物又はその塩を含む、添加剤。
項2.
X1及びX2が、複素環基である項1に記載の添加剤。
項3.
複素環基がピリジル基又はフラニル基である項2に記載の添加剤。
項4.
複素環基が、2-ピリジル基又は3-ピリジル基である項2に記載の添加剤。
項5.
ゴム成分が、ジエン系ゴムである項1~4のいずれか一項に記載の添加剤。
項6.
ゴム成分、及び項1~5のいずれか一項に記載の添加剤を含むゴム混合物を用いて作製された変性ポリマー。
項7.
ゴム成分が、ジエン系ゴムである項6に記載の変性ポリマー。
項8.
ジエン系ゴムに、項1~5のいずれか一項に記載の添加剤を用いて処理された変性ポリマー。
項9.
ジエン系ゴムに、項1~5のいずれか一項に記載の添加剤を処理して得られる変性ポリマー。
項10.
ジエン系ゴムが、天然ゴム及び/又は合成ジエン系ゴムである項7~9のいずれか一項に記載の変性ポリマー。
項11.
合成ジエン系ゴムが、スチレン-ブタジエン共重合体ゴム、ブタジエンゴム、イソプレンゴム、ニトリルゴム、クロロプレンゴム、エチレン-プロピレン-ジエン三元共重合体ゴム、スチレン-イソプレン-スチレン三元ブロック共重合体ゴム、及びスチレン-ブタジエン-スチレン三元ブロック共重合体ゴムからなる群より選ばれる少なくとも一つである項10に記載の変性ポリマー。
項12.
ジエン系ゴムが、天然ゴム、イソプレンゴム、スチレン-ブタジエン共重合体ゴム、及びブタジエンゴムからなる群より選ばれる少なくとも一つである項10に記載の変性ポリマー。
項13.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及びブタジエンゴムからなる群より選ばれる少なくとも一つを50~100質量部含有する項11又は12に記載の変性ポリマー。
項14.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及びブタジエンゴムからなる群より選ばれる少なくとも一つを75~100質量部含有する項11~13のいずれか一項に記載の変性ポリマー。
項15.
下記式(2)~(12)で表される化合物構造から選ばれる少なくとも1つを有する変性ポリマー。 [Wherein, X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
The additive containing the tetrazine compound or its salt represented by these.
Item 4.
Item 5.
Item 5. The additive according to any one of
Item 6.
6. A modified polymer produced using a rubber mixture comprising a rubber component and the additive according to any one of
Item 7.
Item 7. The modified polymer according to Item 6, wherein the rubber component is a diene rubber.
Item 6. A modified polymer obtained by treating a diene rubber with the additive according to any one of
Item 9.
Item 6. A modified polymer obtained by treating a diene rubber with the additive according to any one of
Item 11.
Synthetic diene rubber is styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene-diene terpolymer rubber, styrene-isoprene-styrene terpolymer rubber. Item 11. The modified polymer according to
Item 12.
Item 11. The modified polymer according to
Item 13.
Item 13. The modified polymer according to Item 11 or 12, wherein 50 to 100 parts by mass of at least one selected from the group consisting of styrene-butadiene copolymer rubber and butadiene rubber is contained in 100 parts by mass of the rubber component.
Item 14.
Item 14. The modified polymer according to any one of Items 11 to 13, wherein 75 to 100 parts by mass of at least one selected from the group consisting of styrene-butadiene copolymer rubber and butadiene rubber is contained in 100 parts by mass of the rubber component.
Item 15.
A modified polymer having at least one selected from compound structures represented by the following formulas (2) to (12).
項16.
ゴム成分、項1~5のいずれか一項に記載の添加剤、並びに無機充填材及び/又はカーボンブラックを含むゴム組成物。
項17.
項6~15のいずれか一項に記載の変性ポリマー、並びに無機充填材及び/又はカーボンブラックを含むゴム組成物。
項18.
ゴム成分100質量部に対して、項1~5のいずれか一項に記載の添加剤を0.1~10質量部含有する項16又は17に記載のゴム組成物。
項19.
無機充填材がシリカを含む、項16~18のいずれか一項に記載のゴム組成物。
項20.
ゴム成分100質量部に対して、シリカを20~120質量部含有する項19に記載のゴム組成物。
項21.
ゴム成分100質量部に対して、シリカを40~120質量部含有する項19に記載のゴム組成物。
項22.
ゴム成分が、ジエン系ゴムである項16~21のいずれか一項に記載のゴム組成物。
項23.
ジエン系ゴムが、天然ゴム及び/又は合成ジエン系ゴムである項22に記載のゴム組成物。
項24.
合成ジエン系ゴムが、スチレン-ブタジエン共重合体ゴム、ブタジエンゴム、イソプレンゴム、ニトリルゴム、クロロプレンゴム、エチレン-プロピレン-ジエン三元共重合体ゴム、スチレン-イソプレン-スチレン三元ブロック共重合体ゴム、及びスチレン-ブタジエン-スチレン三元ブロック共重合体ゴムからなる群より選ばれる少なくとも一つである項23に記載のゴム組成物。
項25.
ジエン系ゴムが、天然ゴム、イソプレンゴム、スチレン-ブタジエン共重合体ゴム、及びブタジエンゴムからなる群より選ばれる少なくとも一つである項23に記載のゴム組成物。
項26.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及びブタジエンゴムからなる群より選ばれる少なくとも一つを50~100質量部含有する項24又は25に記載のゴム組成物。
項27.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及びブタジエンゴムからなる群より選ばれる少なくとも一つを75~100質量部含有する項24又25に記載のゴム組成物。
項28.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及び/又はブタジエンゴムが50~100質量部、シリカ20~120質量部、及び項1~5のいずれか一項に記載の添加剤0.1~10質量部を含有するゴム組成物。
項29.
ゴム成分100質量部中、スチレン-ブタジエン共重合体ゴム及び/又はブタジエンゴムが75~100質量部、シリカ20~120質量部、及び項1~5のいずれか一項に記載の添加剤0.1~10質量部を含有するゴム組成物。
項30.
トレッド部、サイドウォール部、ビードエリア部、ベルト部、カーカス部及びショルダー部から選ばれる少なくとも一つの部材に用いられる、項16~29のいずれか一項に記載のゴム組成物。
項31.
トレッド部及びサイドウォール部からなる群から選ばれる少なくとも一つの部材に用いられる、項16~29のいずれか一項に記載のゴム組成物。
項32.
トレッド部の部材に用いられる、項16~29のいずれか一項に記載のゴム組成物。
項33.
項16~29のいずれか一項に記載のゴム組成物を用いて作製されたタイヤ。
項34.
ゴム成分、項1~5のいずれか一項に記載の添加剤、及び無機充填材及び/又はカーボンブラックを含む原料成分を混合する工程(A)、並びに
工程(A)で得られる混合物、及び加硫剤を混合する工程(B)を含む、ゴム組成物の製造方法。
項35.
工程(A)が、ゴム成分、及び項1~5のいずれか一項に記載の添加剤を混合する工程(A-1)、並びに
工程(A-1)で得られた混合物、及び無機充填材及び/又はカーボンブラックを混合する工程(A-2)である、項34に記載の製造方法。
項36.
一般式(1): [Wherein, X 1 and X 2 are the same as those in
Item 16.
A rubber composition comprising a rubber component, the additive according to any one of
Item 17.
Item 16. A rubber composition comprising the modified polymer according to any one of Items 6 to 15, and an inorganic filler and / or carbon black.
Item 18.
Item 18. The rubber composition according to Item 16 or 17, comprising 0.1 to 10 parts by mass of the additive according to any one of
Item 19.
Item 19. The rubber composition according to any one of Items 16 to 18, wherein the inorganic filler contains silica.
Item 21.
Item 22.
Item 22. The rubber composition according to any one of Items 16 to 21, wherein the rubber component is a diene rubber.
Item 23.
Item 23. The rubber composition according to Item 22, wherein the diene rubber is natural rubber and / or synthetic diene rubber.
Synthetic diene rubber is styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene-diene terpolymer rubber, styrene-isoprene-styrene terpolymer rubber.
The additive according to any one of
The additive according to any one of 75 to 100 parts by mass of styrene-butadiene copolymer rubber and / or butadiene rubber, 20 to 120 parts by mass of silica, and 1 to 5 of 100 parts by mass of the rubber component. A rubber composition containing 1 to 10 parts by mass.
Step (A) of mixing a rubber component, an additive according to any one of
Step (A) is a step of mixing the rubber component and the additive according to any one of
General formula (1):
で表されるテトラジン化合物又はその塩を含む、分散剤。
項37.
一般式(1): [Wherein, X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
The dispersing agent containing the tetrazine compound or its salt represented by these.
General formula (1):
で表されるテトラジン化合物又はその塩を含む、低発熱化剤。
項38.
一般式(1): [Wherein, X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
A low exothermic agent comprising a tetrazine compound represented by the formula:
General formula (1):
で表されるテトラジン化合物又はその塩を含む、発熱防止剤。
項39.
一般式(1): [Wherein, X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
An antipyretic agent comprising a tetrazine compound represented by the formula:
General formula (1):
で表されるテトラジン化合物又はその塩を含む、発熱抑制剤。 [Wherein, X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
The exothermic inhibitor containing the tetrazine compound or its salt represented by these.
本発明のゴム成分に低発熱性を付与するための添加剤(以下、「本発明の添加剤」ということもある)は、下記一般式(1)で表される化合物又はその塩(以下、「テトラジン化合物(1)」ということもある。)を含む。 1. Additive for imparting low exothermic property to rubber component Additive for imparting low exothermic property to the rubber component of the present invention (hereinafter sometimes referred to as "additive of the present invention") is represented by the following general formula ( 1) or a salt thereof (hereinafter sometimes referred to as “tetrazine compound (1)”).
1,2,4,5-テトラジン、
3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン、
3,6-ビス(3-ピリジル)-1,2,4,5-テトラジン、
3,6-ビス(4-ピリジル)-1,2,4,5-テトラジン、
3,6-ジフェニル-1,2,4,5-テトラジン、
3,6-ジベンジル-1,2,4,5-テトラジン、
3,6-ビス(2-フラニル)-1,2,4,5-テトラジン、
3-メチル-6-(3-ピリジル)-1,2,4,5-テトラジン、
3,6-ビス(3,5-ジメチル-1-ピラゾリル)-1,2,4,5-テトラジン、
3,6-ビス(2-チエニル)-1,2,4,5-テトラジン、
3-メチル-6-(2-ピリジル)-1,2,4,5-テトラジン、
3,6-ビス(4-ヒドロキシフェニル)-1,2,4,5-テトラジン、
3,6-ビス(3-ヒドロキシフェニル)-1,2,4,5-テトラジン、
3,6-ビス(2-ピリミジニル)-1,2,4,5-テトラジン、
3,6-ビス(2-ピラジル)-1,2,4,5-テトラジン等が挙げられる。 Specifically, as the tetrazine compound (1), for example,
1,2,4,5-tetrazine,
3,6-bis (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-pyridyl) -1,2,4,5-tetrazine,
3,6-diphenyl-1,2,4,5-tetrazine,
3,6-dibenzyl-1,2,4,5-tetrazine,
3,6-bis (2-furanyl) -1,2,4,5-tetrazine,
3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine,
3,6-bis (2-thienyl) -1,2,4,5-tetrazine,
3-methyl-6- (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (3-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (2-pyrimidinyl) -1,2,4,5-tetrazine,
Examples include 3,6-bis (2-pyrazyl) -1,2,4,5-tetrazine.
本明細書において、ゴム成分としては、特に制限はなく、例えば、天然ゴム(NR)、合成ジエン系ゴム、及び天然ゴムと合成ジエン系ゴムとの混合物、並びにこれら以外の非ジエン系ゴムが挙げられる。 Rubber component In the present specification, the rubber component is not particularly limited. For example, natural rubber (NR), synthetic diene rubber, a mixture of natural rubber and synthetic diene rubber, and other non-diene rubbers Is mentioned.
本発明の変性ポリマーは、ジエン系ゴム、及び上記本発明の添加剤を含むゴム混合物を用いて作製される。 2. Modified Polymer The modified polymer of the present invention is produced using a rubber mixture containing a diene rubber and the additive of the present invention.
テトラジン化合物(1)と、ゴム成分中の二重結合との間で逆電子要請型Aza-Diels-Alder反応が進行する。 [Reaction mechanism between rubber component and additive of the present invention]
A reverse electron request type Aza-Diels-Alder reaction proceeds between the tetrazine compound (1) and the double bond in the rubber component.
反応式-1 Specifically, as the reactions shown in the following reaction formulas -1 to 4 proceed, the tetrazine compound (1) is bonded to the double bond site of the diene rubber to form a six-membered ring structure, A modified polymer is produced.
Reaction Formula-1
反応式-1においては、式(A-1)で表されるジエン系ゴムの二重結合部位とテトラジン化合物(1)との逆電子要請型Aza-Diels-Alder反応によって、式(B-1)で表されるビシクロ環構造を形成する。このビシクロ環構造中の-N=N-部は、脱窒素化が容易に進行し、式(C-1)、(C-2)又は(C-3)で表される六員環構造を形成するが、更に空気中の酸素によって酸化され、式(2)で表される六員環構造を有する、変性ポリマーが製造される。
反応式-2 [Wherein, X 1 and X 2 are the same as above. ]
In the reaction formula-1, the reverse electron request type Aza-Diels-Alder reaction between the double bond site of the diene rubber represented by the formula (A-1) and the tetrazine compound (1) results in the formula (B-1 The bicyclo ring structure represented by this is formed. The —N═N— moiety in this bicyclo ring structure is easily denitrogenated, and has a six-membered ring structure represented by the formula (C-1), (C-2) or (C-3). A modified polymer is formed which has a six-membered ring structure represented by formula (2) by being further oxidized by oxygen in the air.
Reaction formula-2
反応式-2においては、反応式-1と同様に、式(A-2)で表されるジエン系ゴムの二重結合部位とテトラジン化合物(1)とから、式(B-2)又は(B-2’)で表されるビシクロ環構造、次いで式(C-4)乃至(C-9)で表される六員環構造を形成した後、式(3)又は(4)で表される六員環構造を有する、変性ポリマーが製造される。
反応式-3 [Wherein, X 1 and X 2 are the same as above. ]
In the reaction formula-2, as in the reaction formula-1, the double bond site of the diene rubber represented by the formula (A-2) and the tetrazine compound (1) are used to formula (B-2) or ( B-2 ′) and then a six-membered ring structure represented by formulas (C-4) to (C-9), and then represented by formula (3) or (4) A modified polymer having a six-membered ring structure is produced.
Reaction formula-3
反応式-3においては、式(A-3)で表されるジエン系ゴムの二重結合部位とテトラジン化合物(1)との逆電子要請型Aza-Diels-Alder反応により、式(B-3)又は(B-3’)で表されるビシクロ環構造を形成した後、脱窒素化により式(5)乃至(8)で表される六員環構造を有する、変性ポリマーが製造される。なお、式(A-3)で表されるジエン系ゴムの二重結合部位上Rがハロゲン原子である場合は、そのハロゲン原子の脱離が生じることがあり、その場合は、酸化反応により式(2)で表される六員環構造を有する、変性ポリマーが製造される。
反応式-4 [Wherein, X 1 and X 2 are the same as above. R represents an alkyl group or a halogen atom. ]
In the reaction formula-3, a reverse electron request type Aza-Diels-Alder reaction between the double bond site of the diene rubber represented by the formula (A-3) and the tetrazine compound (1) results in the formula (B-3 ) Or (B-3 ′), a modified polymer having a six-membered ring structure represented by formulas (5) to (8) is produced by denitrogenation. In addition, when R on the double bond site of the diene rubber represented by the formula (A-3) is a halogen atom, the elimination of the halogen atom may occur. A modified polymer having a six-membered ring structure represented by (2) is produced.
Reaction formula-4
反応式-4においては、反応式-3の反応と同様に、式(A-4)で表されるジエン系ゴムの二重結合部位とテトラジン化合物(1)との反応により、式(B-4)又は、(B-4’)で表されるビシクロ環構造を形成した後、式(9)乃至(12)で表される六員環構造を有する、変性ポリマーが製造される。 [Wherein, X 1 , X 2 and R are the same as above. ]
In the reaction formula-4, as in the reaction of the reaction formula-3, the reaction of the double bond site of the diene rubber represented by the formula (A-4) with the tetrazine compound (1) results in the reaction of the formula (B- 4) Or, after forming a bicyclo ring structure represented by (B-4 ′), a modified polymer having a six-membered ring structure represented by formulas (9) to (12) is produced.
本発明の添加剤を構成するテトラジン化合物(1)の窒素原子がシリカと高い親和性を示し、また、ゴム成分とテトラジン化合物(1)とが反応して生成した変性ポリマーは、そのテトラジン化合物由来の窒素原子の存在により、さらにシリカとの親和性が改善されると推測される。特に、テトラジン化合物(1)の3位(X1基)及び6位(X2基)に、ヘテロ原子を有する置換基又は極性基を導入することで、シリカとの親和性が増強されることが推測される。よって、本発明の添加剤によって、ゴム成分中にシリカが分散されると考えられる。 [Silica dispersion mechanism]
The modified polymer produced by the reaction of the rubber component and the tetrazine compound (1) with the nitrogen atom of the tetrazine compound (1) constituting the additive of the present invention has high affinity with silica. It is presumed that the affinity for silica is further improved by the presence of nitrogen atoms. In particular, the affinity with silica is enhanced by introducing a substituent or a polar group having a hetero atom into the 3-position (X 1 group) and the 6-position (X 2 group) of the tetrazine compound (1). Is guessed. Therefore, it is considered that silica is dispersed in the rubber component by the additive of the present invention.
本発明の変性ポリマーの製造方法としては、特に制限はない。本発明の変性ポリマーは、例えば、天然ゴム及び合成ジエン系ゴムからなる群より選ばれる少なくとも1種のゴム成分、及びテトラジン化合物(1)を含むゴム混合物を用いて作製される。 The method for producing a modified polymer of the production method the present invention modified polymers is not particularly limited. The modified polymer of the present invention is produced using, for example, a rubber mixture containing at least one rubber component selected from the group consisting of natural rubber and synthetic diene rubber and a tetrazine compound (1).
ゴム成分が液状(液体)である場合は、該ゴム成分の溶液又は乳液(懸濁液)と、テトラジン化合物(1)とを加熱条件下で混合する方法(液状混合方法)等が挙げられる。 As a specific method for producing the modified polymer of the present invention, when the rubber component is solid, the rubber component and the tetrazine compound (1) are kneaded under heating conditions (kneading method);
When the rubber component is liquid (liquid), a method of mixing the rubber component solution or emulsion (suspension) and the tetrazine compound (1) under heating conditions (liquid mixing method) and the like can be mentioned.
本発明のゴム組成物は、ゴム成分、上記本発明の添加剤、並びに無機充填材及び/又はカーボンブラックを含んでいる。 3. Rubber composition The rubber composition of the present invention contains a rubber component, the additive of the present invention, and an inorganic filler and / or carbon black.
無機充填材としては、ゴム工業界において、通常使用される無機化合物であれば、特に制限はない。使用できる無機化合物としては、例えば、シリカ;γ-アルミナ、α-アルミナ等のアルミナ(Al2O3);ベーマイト、ダイアスポア等のアルミナ一水和物(Al2O3・H2O);ギブサイト、バイヤライト等の水酸化アルミニウム[Al(OH)3];炭酸アルミニウム[Al2(CO3)2]、水酸化マグネシウム[Mg(OH)2]、酸化マグネシウム(MgO)、炭酸マグネシウム(MgCO3)、タルク(3MgO・4SiO2・H2O)、アタパルジャイト(5MgO・8SiO2・9H2O)、チタン白(TiO2)、チタン黒(TiO2n-1)、酸化カルシウム(CaO)、水酸化カルシウム[Ca(OH)2]、酸化アルミニウムマグネシウム(MgO・Al2O3)、クレー(Al2O3・2SiO2)、カオリン(Al2O3・2SiO2・2H2O)、パイロフィライト(Al2O3・4SiO2・H2O)、ベントナイト(Al2O3・4SiO2・2H2O)、ケイ酸アルミニウム(Al2SiO5、Al4・3SiO4・5H2O等)、ケイ酸マグネシウム(Mg2SiO4、MgSiO3等)、ケイ酸カルシウム(Ca2・SiO4等)、ケイ酸アルミニウムカルシウム(Al2O3・CaO・2SiO2等)、ケイ酸マグネシウムカルシウム(CaMgSiO4)、炭酸カルシウム(CaCO3)、酸化ジルコニウム(ZrO2)、水酸化ジルコニウム[ZrO(OH)2・nH2O]、炭酸ジルコニウム[Zr(CO3)2]、アクリル酸亜鉛、メタクリル酸亜鉛、各種ゼオライトのように電荷を補正する水素、アルカリ金属又はアルカリ土類金属を含む結晶性アルミノケイ酸塩等が挙げられる。これらの無機充填材は、ゴム成分との親和性を向上させるために、該無機充填材の表面が有機処理されていてもよい。 The inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry. Examples of inorganic compounds that can be used include silica; alumina such as γ-alumina and α-alumina (Al 2 O 3 ); alumina monohydrate such as boehmite and diaspore (Al 2 O 3 .H 2 O); gibbsite Aluminum hydroxide [Al (OH) 3 ], such as bayerite; aluminum carbonate [Al 2 (CO 3 ) 2 ], magnesium hydroxide [Mg (OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), Talc (3MgO · 4SiO 2 · H 2 O), attapulgite (5MgO · 8SiO 2 · 9H 2 O), titanium white (TiO 2 ), titanium black (TiO 2n-1 ), calcium oxide (CaO), hydroxylated Calcium [Ca (OH) 2 ], aluminum magnesium oxide (MgO · Al 2 O 3 ), clay (Al 2 O 3 · 2SiO 2 ), kaolin (Al 2 O 3 · 2SiO 2 · 2H 2 O), pyrophyllite (Al 2 O 3 · 4SiO 2 · H 2 O), bentonite (Al 2 O 3 · 4SiO 2 · 2H) 2 O), aluminum silicate (Al 2 SiO 5 , Al 4 .3SiO 4 .5H 2 O, etc.), magnesium silicate (Mg 2 SiO 4 , MgSiO 3 etc.), calcium silicate (Ca 2 · SiO 4 etc.) , Aluminum calcium silicate (Al 2 O 3 · CaO · 2SiO 2 etc.), magnesium calcium silicate (CaMgSiO 4 ), calcium carbonate (CaCO 3 ), zirconium oxide (ZrO 2 ), zirconium hydroxide [ZrO (OH) 2 · nH 2 O], zirconium carbonate [Zr (CO 3) 2] , zinc acrylate, zinc methacrylate, Hydrogen for correcting the charge as the seed zeolites, crystalline aluminosilicates such as containing alkali metal or alkaline earth metal. In order to improve the affinity of the inorganic filler with the rubber component, the surface of the inorganic filler may be organically treated.
カーボンブラックとしては、特に制限はなく、例えば、市販品のカーボンブラック、Carbon-Silica Dual phase filler等が挙げられる。ゴム成分にカーボンブラックを含有することにより、ゴムの電気抵抗を下げて、帯電を抑止する効果、さらにゴムの強度を向上させる効果を享受できる。 The carbon black carbon black is not particularly limited, and examples thereof include commercially available carbon black and Carbon-Silica Dual phase filler. By containing carbon black in the rubber component, it is possible to enjoy the effect of reducing the electrical resistance of the rubber and suppressing charging, and the effect of improving the strength of the rubber.
本発明のゴム組成物には、上記テトラジン化合物(1)並びに無機充填材及び/又はカーボンブラック以外にも、ゴム工業界で通常使用される配合剤、例えば、老化防止剤、オゾン防止剤、軟化剤、加工助剤、ワックス、樹脂、発泡剤、オイル、ステアリン酸、亜鉛華(ZnO)、加硫促進剤、加硫遅延剤、加硫剤(硫黄)等を、本発明の目的を害しない範囲内で適宜選択して配合することができる。これら配合剤としては、市販品を好適に使用することができる。 Other compounding agents In addition to the tetrazine compound (1) and the inorganic filler and / or carbon black, the rubber composition of the present invention includes compounding agents commonly used in the rubber industry, such as anti-aging agents, ozone, and the like. Inhibitors, softeners, processing aids, waxes, resins, foaming agents, oils, stearic acid, zinc white (ZnO), vulcanization accelerators, vulcanization retarders, vulcanizing agents (sulfur), etc. It can be appropriately selected and blended within a range that does not impair the purpose. As these compounding agents, commercially available products can be suitably used.
オレフィン系のシランカップリング剤としては、例えば、ジメトキシメチルビニルシラン、ビニルトリメトキシシラン、ジメチルエトキシビニルシラン、ジエトキシメチルビニルシラン、トリエトキシビニルシラン、ビニルトリス(2-メトキシエトキシ)シラン、アリルトリメトキシシラン、アリルトリエトキシシラン、p-スチリルトリメトキシシラン、3-(メトキシジメトキシジメチルシリル)プロピルアクリレート、3-(トリメトキシシリル)プロピルアクリレート、3-[ジメトキシ(メチル)シリル]プロピルメタクリレート、3-(トリメトキシシリル)プロピルメタクリレート、3-[ジメトキシ(メチル)シリル]プロピルメタクリレート、3-(トリエトキシシリル)プロピルメタクリレート、3-[トリス(トリメチルシロキシ)シリル]プロピルメタクリレート等を挙げることができる。 Examples of the thiol-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like.
Examples of olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, allyltri Ethoxysilane, p-styryltrimethoxysilane, 3- (methoxydimethoxydimethylsilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (trimethoxysilyl) Propyl methacrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- [tris (tri Chirushirokishi) silyl] propyl methacrylate, and the like.
本発明のゴム組成物の用途としては、特に制限はなく、例えば、タイヤ、防振ゴム、コンベアベルト、これらのゴム部分等が挙げられる。中でも、好ましい用途は、タイヤである。 Use of rubber composition The use of the rubber composition of the present invention is not particularly limited, and examples thereof include tires, anti-vibration rubbers, conveyor belts, and rubber portions thereof. Among these, a preferable use is a tire.
本発明のゴム組成物の製造方法としては、特に制限されない。本発明のゴム組成物の製造方法は、例えば、ゴム成分、本発明の添加剤、並びに無機充填材及び/又はカーボンブラックを含む原料成分を混練する工程(A)、並びに工程(A)で得られる混合物、及び加硫剤を混練する工程(B)を含んでいる。 Production method of rubber composition The production method of the rubber composition of the present invention is not particularly limited. The rubber composition production method of the present invention is obtained, for example, in the step (A) of kneading the rubber component, the additive of the present invention, and the raw material component containing an inorganic filler and / or carbon black, and the step (A). And a step (B) of kneading the vulcanizing agent.
工程(A)は、ゴム成分、本発明の添加剤、並びに無機充填材及び/又はカーボンブラックを含む原料成分を混練する工程であり、加硫剤を配合する前の工程であることを意味している。 Process (A)
The step (A) is a step of kneading the rubber component, the additive of the present invention, and the raw material component containing the inorganic filler and / or carbon black, and means that it is a step before blending the vulcanizing agent. ing.
工程(B)は、工程(A)で得られる混合物、及び加硫剤を混合する工程(B)であり、混練の最終段階を意味している。 Process (B)
Step (B) is a step (B) in which the mixture obtained in step (A) and the vulcanizing agent are mixed, and means the final stage of kneading.
本発明のタイヤは、上記本発明の添加剤、ゴム組成物又は変性ポリマーを用いて作製されたタイヤである。 4). Tire The tire of the present invention is a tire produced using the additive, rubber composition or modified polymer of the present invention.
200mL四つ口フラスコに、3-シアノピリジン24g(0.23モル)、水加ヒドラジン15g(1.3当量)、及びメタノール48mLを加え、室温で撹拌した。次いで、この混合物に、硫黄3.6g(15重量%)を加え、還流管を装着して外温70℃にて一晩加熱撹拌した。この反応液を氷冷し、結晶を濾過して少量の冷メタノールで洗浄した。粗結晶を減圧下乾燥し、橙色のジヒドロテトラジン粗結晶19gを得た。 Production Example 1: Production of 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine (1a) In a 200 mL four-necked flask, 24 g (0.23 mol) of 3-cyanopyridine was added with water. Hydrazine (15 g, 1.3 equivalents) and methanol (48 mL) were added, and the mixture was stirred at room temperature. Next, 3.6 g (15% by weight) of sulfur was added to this mixture, and a reflux tube was attached, followed by heating and stirring at an external temperature of 70 ° C. overnight. The reaction solution was ice-cooled, and the crystals were filtered and washed with a small amount of cold methanol. The crude crystals were dried under reduced pressure to obtain 19 g of orange dihydrotetrazine crude crystals.
融点:200℃、
1H-NMR(300MHz,CDCl3,δppm):
7.59(ddd,J =0.9,5.1,7.8 Hz,2H),8.89-8.96(m,4H),9.88(dd,J =0.9,2.4Hz,2H) 17.8 g of the obtained crude crystals were dissolved in 178 g (40 equivalents) of acetic acid, and sulfur was removed by filtration. A dihydrotetrazine acetic acid solution and 178 mL of distilled water were added to a 1 L four-necked eggplant flask and stirred under ice cooling. 15.5 g (3 equivalents) of sodium nitrite was dissolved in 35 mL of distilled water, added dropwise to the reaction solution over about 1 hour, and stirred overnight at room temperature. The precipitated crystals were filtered and the crystals were neutralized with 10% multilayer water to obtain crude crystals. The crude crystals were purified with a silica gel column (ethyl acetate) to obtain 8.4 g (red purple, needle-like crystals) of the title tetrazine compound (1a).
Melting point: 200 ° C.
1 H-NMR (300 MHz, CDCl 3 , δ ppm):
7.59 (ddd, J = 0.9, 5.1, 7.8 Hz, 2H), 8.89-8.96 (m, 4H), 9.88 (dd, J = 0.9, 2 .4Hz, 2H)
500mL四つ口フラスコに、ベンゾニトリル120g(1.16モル)、水加ヒドラジン76g(1.3当量)、及びメタノール348mLを加え、室温で撹拌した。次いで、この混合物に、硫黄10g(8.6重量%)を加え、還流管を装着して外温70℃にて一晩加熱撹拌した。得られた反応液を氷冷し、結晶を濾過し、少量の冷メタノールで洗浄した。得られた粗結晶を2.5Lの温メタノールに溶解し、不溶物を濾過した後、濾液の溶媒を留去した。得られた粗結晶を減圧下乾燥し、黄色のジヒドロテトラジン粗結晶48gを得た。 Production Example 2: Production of 3,6-diphenyl-1,2,4,5-tetrazine (1d) A 500 mL four-necked flask was charged with 120 g (1.16 mol) of benzonitrile and 76 g (1.3 equivalents) of hydrazine hydrate. ) And 348 mL of methanol were added and stirred at room temperature. Next, 10 g (8.6% by weight) of sulfur was added to the mixture, and a reflux tube was attached, followed by heating and stirring overnight at an external temperature of 70 ° C. The resulting reaction solution was ice-cooled, and the crystals were filtered and washed with a small amount of cold methanol. The obtained crude crystals were dissolved in 2.5 L of warm methanol, insoluble matters were filtered off, and then the solvent of the filtrate was distilled off. The obtained crude crystals were dried under reduced pressure to obtain 48 g of yellow dihydrotetrazine crude crystals.
融点:166℃、
1H-NMR(300MHz,CDCl3,δppm):
7.58-7.68(m,6H),8.64-8.69(m,4H) To a 300 mL four-necked eggplant flask, 4.8 g of crude crystals, 48 mL of acetic acid and 48 mL of distilled water were added and stirred under ice cooling. Sodium nitrite 4.2 g (3 equivalents) was dissolved in distilled
Melting point: 166 ° C,
1 H-NMR (300 MHz, CDCl 3 , δ ppm):
7.58-7.68 (m, 6H), 8.64-8.69 (m, 4H)
300mL四つ口フラスコに、フェニルアセトニトリル58.5g(0.5モル)、水加ヒドラジン100g(4.0当量)を加え、室温で撹拌した。次いで、この混合物に、硫黄9.0g(15重量%)を加え、還流管を装着して外温90℃にて一晩加熱撹拌した。この反応液を氷冷し、蒸留水100mLを加えて内容物を薬匙で粉砕した後、結晶を濾過して蒸留水で洗浄した。粗結晶を減圧下乾燥し、白色のジヒドロテトラジンを含む粗結晶61gを得た。 Production Example 3: Production of 3,6-dibenzyl-1,2,4,5-tetrazine (1e) In a 300 mL four-necked flask, 58.5 g (0.5 mol) of phenylacetonitrile and 100 g of hydrazine hydrate (4. 0 equivalents) was added and stirred at room temperature. Next, 9.0 g (15% by weight) of sulfur was added to the mixture, and a reflux tube was attached, and the mixture was heated and stirred overnight at an external temperature of 90 ° C. The reaction solution was ice-cooled, 100 mL of distilled water was added and the contents were pulverized with a shell, and the crystals were filtered and washed with distilled water. The crude crystals were dried under reduced pressure to obtain 61 g of crude crystals containing white dihydrotetrazine.
融点:68℃、
1H-NMR(300MHz,CDCl3,δppm):
4.60(s,4H),7.22-7.35(m,6H),7.39-7.43(m,4H) To the 1 L four-necked eggplant flask, 61 g of the obtained crude crystals, 210 g of acetic acid and 200 mL of distilled water were added and stirred under ice cooling. 23.9 g (1.5 equivalents) of sodium nitrite was dissolved in 100 mL of distilled water, added dropwise to the reaction solution over about 1 hour, and stirred overnight at room temperature. Distilled water (500 mL) was added to the reaction mixture, and the mixture was extracted 3 times with 100 mL of ethyl acetate. The obtained organic layer was washed once with 100 mL of distilled water, once with 200 mL of saturated multilayered water, and once with 200 mL of saturated brine, and then the solvent was distilled off to obtain 48 g of red crude crystals. The crude crystals were purified with a silica gel column (n-hexane: ethyl acetate = 5: 1) to obtain 5.1 g (red, scaly crystals) of the title tetrazine compound (1e).
Melting point: 68 ° C
1 H-NMR (300 MHz, CDCl 3 , δ ppm):
4.60 (s, 4H), 7.22-7.35 (m, 6H), 7.39-7.43 (m, 4H)
50mL3つ口フラスコに、2-フロニトリル3g(0.032モル)、水加ヒドラジン3.3g(2.0当量)、及びエタノール15mLを加え、氷冷下で撹拌した。次いで、この混合物に、硫黄0.3グラム(10重量%)を加え、還流管を装着して外温80℃にて2時間加熱撹拌した。得られた反応液を氷冷し、結晶を濾過した後、減圧下乾燥することで黄色のジヒドロテトラジン粗結晶2.48gを得た。 Production Example 4: Production of 3,6-bis (2-furanyl) -1,2,4,5-tetrazine (1f) To a 50 mL three-necked flask, 3 g (0.032 mol) of 2-furonitrile and
融点:198-199℃、
1H-NMR(500MHz,CDCl3,δppm):
7.81(dd,J = 0.4,1.7Hz,2H),7.67(dd,J = 0.4,3.6Hz,2H),6.72(dd,J = 1.7,3.6Hz,2H) To a 500 mL four-necked eggplant flask, 2.48 g of crude crystals, 150 mL of chloroform, and 35 mL of isoamyl nitrite were added and stirred overnight at room temperature. The solvent was removed by drying under reduced pressure, and 2.39 g of the resulting crude crystals were purified with a silica gel column (chloroform: n-hexane = 3: 1) to obtain 1.31 g (red solid) of the title tetrazine compound (1f). It was.
Melting point: 198-199 ° C
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
7.81 (dd, J = 0.4, 1.7 Hz, 2H), 7.67 (dd, J = 0.4, 3.6 Hz, 2H), 6.72 (dd, J = 1.7, 3.6Hz, 2H)
2L四つ口フラスコに氷冷下で、3-シアノピリジン124.8g(1.2モル)、アセトアミジン塩酸塩567.6g(5.0当量)、水加ヒドラジン564g(10.0当量)を加え、室温で一晩撹拌した。この反応液を氷冷し、結晶を濾過した後、減圧下乾燥することで粗結晶431.2gを得た。 Production Example 5 Production of 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine (1 g) In a 2 L four-necked flask under ice cooling, 124.8 g (1 0.2 mol), 567.6 g (5.0 equivalents) of acetamidine hydrochloride, and 564 g (10.0 equivalents) of hydrazine hydrate were added and stirred overnight at room temperature. The reaction solution was ice-cooled, and the crystals were filtered and dried under reduced pressure to obtain 431.2 g of crude crystals.
融点:102℃、
1H-NMR(500MHz,CDCl3,δppm):
9.80(m,J = 1.6Hz,1H),8.84-8.87(m,2H),7.55(ddd,J = 0.7,4.9,8.0Hz,1H),3.14(s,3H) In a 5 L beaker, 431.2 g of crude crystals, 720 g (10 equivalents) of acetic acid and 200 mL of distilled water were added and stirred under ice cooling. 300 g (3.7 equivalents) of sodium nitrite was dissolved in 720 mL of distilled water, added dropwise to the reaction solution over about 1 hour, and stirred for 1 hour under ice cooling. The reaction solution was neutralized with aqueous sodium bicarbonate and extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 156.54 g of crude crystals. This was purified by a silica gel column (n-hexane: ethyl acetate = 3: 1) to obtain 71.81 g (red purple, crystal) of the title tetrazine compound (1 g).
Melting point: 102 ° C.
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
9.80 (m, J = 1.6 Hz, 1H), 8.84-8.87 (m, 2H), 7.55 (ddd, J = 0.7, 4.9, 8.0 Hz, 1H) , 3.14 (s, 3H)
2000mL四つ口フラスコに、アミノグアニジン塩酸塩250g(2.26モル)、水加ヒドラジン249g(2.2当量)、及びメタノール400mLを加え、24時間加熱還流した。室温に冷却した後、固体をろ過し、メタノールで洗浄した。得られた固体を減圧乾燥し、白色のトリアミノグアニジン塩酸塩286g(収率90%)を得た。 Production Example 6 Production of 3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine (1h) In a 2000 mL four-necked flask, 250 g of aminoguanidine hydrochloride (2. 26 mol), hydrazine hydrate (249 g, 2.2 equivalents), and methanol (400 mL) were added, and the mixture was heated to reflux for 24 hours. After cooling to room temperature, the solid was filtered and washed with methanol. The obtained solid was dried under reduced pressure to obtain 286 g (yield 90%) of white triaminoguanidine hydrochloride.
融点:220℃、
1H-NMR(300MHz,CDCl3,δppm):
2.40(s,6H),2.72(s,6H),6.20(s,2H) To a 5000 mL beaker, 65 g (0.24 mol) of synthesized dihydrotetrazine, 350 mL of distilled water, and 137 mL (10.0 equivalents) of acetic acid were added and cooled in an ice bath. Thereto, 33 g (2.0 equivalents) of sodium nitrite dissolved in 50 mL of distilled water was added dropwise. After stirring for 2 hours in an ice bath, the temperature was raised to room temperature, and stirring was continued for another 4 hours. Thereafter, the solid was filtered and washed with distilled water and n-hexane. The obtained solid was dried under reduced pressure to obtain 64 g (yield 98%) of red title tetrazine (1h).
Melting point: 220 ° C.
1 H-NMR (300 MHz, CDCl 3 , δ ppm):
2.40 (s, 6H), 2.72 (s, 6H), 6.20 (s, 2H)
300mL四つ口フラスコに氷冷下で、2-シアノチオフェン21.48g(0.197モル)、硫黄4.3g(20重量%)、エタノール92mL及び水加ヒドラジン20.1g(2.1当量)を加え、65℃で4時間撹拌した。この反応液を氷冷し、結晶を濾過し、蒸留水で洗浄した後、減圧下乾燥することで20.56gの粗結晶を得た。 Production Example 7 Production of 3,6-bis (2-thienyl) -1,2,4,5-tetrazine (1i) In a 300 mL four-necked flask under ice cooling, 21.48 g (0. 197 mol), 4.3 g (20% by weight) of sulfur, 92 mL of ethanol and 20.1 g (2.1 equivalents) of hydrazine hydrate were added, and the mixture was stirred at 65 ° C. for 4 hours. The reaction solution was ice-cooled, the crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 20.56 g of crude crystals.
融点:198℃、
1H-NMR(500MHz,CDCl3,δppm):
8.28(dd,J = 0.9,3.8Hz,2H),7.69(dd,0.9,5.0Hz,2H),7.28(m,2H) In a 1 L beaker, 20.56 g of crude crystals, 59.1 g (5 equivalents) of acetic acid and 60 mL of distilled water were added and stirred under ice cooling. 40.7 g (3 equivalents) of sodium nitrite was dissolved in 80 mL of distilled water, added dropwise to the reaction solution over about 1 hour, and stirred for 5 hours under ice cooling. The reaction solution was neutralized with aqueous sodium bicarbonate and extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 18.7 g of crude crystals. This was purified with a silica gel column (dichloromethane: n-hexane = 2: 1) to obtain 16.8 g (red, crystals) of the title tetrazine compound (1i).
Melting point: 198 ° C
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
8.28 (dd, J = 0.9, 3.8 Hz, 2H), 7.69 (dd, 0.9, 5.0 Hz, 2H), 7.28 (m, 2H)
100mL四つ口フラスコに氷冷下で、2-シアノピリジン5g(0.048モル)、アセトアミジン塩酸塩22.7g(5.0当量)、及び水加ヒドラジン24g(10.0当量)を加え、室温で一晩撹拌した。この反応液を氷冷し、結晶を濾過した。粗結晶を減圧下乾燥することで14.15gの粗結晶を得た。 Production Example 8 Production of 3-methyl, 6- (2-pyridyl) -1,2,4,5-tetrazine (1j) In a 100 mL four-necked flask under ice cooling, 5 g (0.048 ) of 2-cyanopyridine was prepared. Mol), 22.7 g (5.0 equivalents) of acetamidine hydrochloride, and 24 g (10.0 equivalents) of hydrazine hydrate were added and stirred overnight at room temperature. The reaction mixture was ice-cooled and the crystals were filtered. The crude crystals were dried under reduced pressure to obtain 14.15 g of crude crystals.
融点:63℃、
1H-NMR(500MHz,CDCl3,δppm):
8.96(m,1H),8.65(m,1H),7.99(ddd,J = 1.5,7.8,8.3Hz,1H),7.57(ddd,J = 0.7,4.7,7.8Hz,1H),3.17(s,3H) In a 1 L beaker, 14.15 g of crude crystals, 42.5 g (15 equivalents) of acetic acid and 41 mL of distilled water were added and stirred under ice cooling. Sodium nitrite (32.2 g, 10 equivalents) was dissolved in distilled water (60 mL), added dropwise to the reaction solution over about 1 hour, and stirred under ice cooling for 5 hours. The reaction solution was neutralized with aqueous sodium bicarbonate and extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure to obtain 4.74 g of crude crystals. This was purified by a silica gel column (n-hexane: ethyl acetate = 3: 1) to obtain 1.02 g (red, crystals) of the title tetrazine compound (1j).
Melting point: 63 ° C
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
8.96 (m, 1H), 8.65 (m, 1H), 7.9 (ddd, J = 1.5, 7.8, 8.3 Hz, 1H), 7.57 (ddd, J = 0) .7, 4.7, 7.8 Hz, 1H), 3.17 (s, 3H)
300mL3つ口フラスコに、4-ヒドロキシベンゾニトリル50.0g(0.42モル)、及び水加ヒドラジン63.0g(3.0当量)を加え、氷冷下で撹拌した後、70℃で20時間加熱撹拌した。得られた反応液を氷冷し、結晶を濾過した後、減圧下乾燥することで黄色のジヒドロテトラジン粗結晶49.8gを得た。 Production Example 9 Production of 3,6-bis (4-hydroxyphenyl) -1,2,4,5 -tetrazine (1k) In a 300 mL three-necked flask, 50.0 g (0.42 mol) of 4-hydroxybenzonitrile was added. And 63.0 g (3.0 equivalents) of hydrated hydrazine were added and stirred under ice cooling, followed by heating and stirring at 70 ° C. for 20 hours. The resulting reaction solution was ice-cooled, the crystals were filtered, and dried under reduced pressure to obtain 49.8 g of yellow dihydrotetrazine crude crystals.
融点:320℃(分解)、
1H-NMR(300MHz,CDCl3,δppm):
8.36(m,4H),7.03(m,4H) To a 1 L four-necked eggplant flask, 49.8 g of crude crystals and 500 mL of chloroform were added, and oxygen was bubbled for 20 hours while stirring at room temperature. After filtration, the crude crystals were recrystallized from DMF to obtain 52.0 g (red solid) of the title tetrazine compound (1k).
Melting point: 320 ° C. (decomposition)
1 H-NMR (300 MHz, CDCl 3 , δ ppm):
8.36 (m, 4H), 7.03 (m, 4H)
300mL四つ口フラスコに、3-シアノフェノール50g(0.42モル)、水加ヒドラジン42g(2当量)、及び硫黄5g(10重量%)を加え、室温で撹拌した後、還流管を装着し外温50℃にて一晩加熱撹拌した。得られた反応液を氷冷し、結晶を濾過し、少量の冷エタノールで洗浄した。これを減圧下乾燥し、ジヒドロテトラジン粗結晶21.5gを得た。 Production Example 10 Production of 3,6-bis (3-hydroxyphenyl) -1,2,4,5-tetrazine (1 l) In a 300 mL four-necked flask, 50 g (0.42 mol) of 3-cyanophenol, water After adding 42 g (2 equivalents) of hydrazine and 5 g (10% by weight) of sulfur and stirring at room temperature, a reflux tube was attached and the mixture was heated and stirred overnight at an external temperature of 50 ° C. The resulting reaction solution was ice-cooled, and the crystals were filtered and washed with a small amount of cold ethanol. This was dried under reduced pressure to obtain 21.5 g of dihydrotetrazine crude crystals.
融点:304-305.5℃、
1H-NMR(500MHz,d6-DMSO,δppm):
10.01(s,2H),7.98(dd,J = 1.6,7.8Hz,2H),7.94(dd,J = 1.6,1.8Hz,2H),7.49(dd,J = 7.8,8.0Hz,2H),7.09(dd,J = 1.8,8.0Hz,2H) To a 1 L eggplant flask, 21.5 g of crude crystals and 430 mL of ethanol were added and stirred at room temperature. The reaction solution was stirred for 10 hours while bubbling oxygen, and then concentrated under reduced pressure to obtain 21.5 g of crude crystals. This was washed with ethanol and distilled water to obtain 7.3 g (orange, solid) of the title tetrazine compound (1 l).
Melting point: 304-305.5 ° C.
1 H-NMR (500 MHz, d 6 -DMSO, δ ppm):
10.1 (s, 2H), 7.98 (dd, J = 1.6, 7.8 Hz, 2H), 7.94 (dd, J = 1.6, 1.8 Hz, 2H), 7.49 (Dd, J = 7.8, 8.0 Hz, 2H), 7.09 (dd, J = 1.8, 8.0 Hz, 2H)
200mL四つ口フラスコに、2-シアノピリミジン25g(0.238モル)、水加ヒドラジン23.8g(2当量)、酢酸28.6g(2当量)、及びジメチルスルホキシド(8.3mL)を加え、室温で撹拌した。この混合液を外温50℃にて一晩加熱撹拌した。この反応液を氷冷し、結晶を濾過、減圧下乾燥し、ジヒドロテトラジン粗結晶30.1gを得た。 Production Example 11 Production of 3,6-bis (2-pyrimidinyl) -1,2,4,5-tetrazine (1 m) In a 200 mL four-necked flask, 25 g (0.238 mol) of 2-cyanopyrimidine was added with water. Hydrazine 23.8 g (2 equivalents), acetic acid 28.6 g (2 equivalents), and dimethyl sulfoxide (8.3 mL) were added, and the mixture was stirred at room temperature. The mixture was heated and stirred overnight at an external temperature of 50 ° C. This reaction solution was ice-cooled, and the crystals were filtered and dried under reduced pressure to obtain 30.1 g of dihydrotetrazine crude crystals.
融点:264-267℃、
1H-NMR(500MHz,CDCl3,δppm):
9.18(d,J =4.9 Hz,4H),7.63(t,J =4.9 Hz,2H) To a 5 L beaker were added 30.1 g of crude crystals, 500 mL of tetrahydrofuran, and 3.8 L (8 equivalents) of 0.5N hydrochloric acid, and the mixture was stirred under ice cooling. 32.8 g (2 equivalents) of sodium nitrite was dissolved in 60 mL of distilled water, added dropwise to the reaction solution over about 0.5 hour, and stirred for 1 hour under ice cooling. Extraction with methylene chloride and 3.4 g of crude crystals obtained by concentration under reduced pressure were washed with 250 mL of acetone to obtain 3.2 g (purple, solid) of the title tetrazine compound (1 m).
Melting point: 264-267 ° C
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
9.18 (d, J = 4.9 Hz, 4H), 7.63 (t, J = 4.9 Hz, 2H)
2L四つ口フラスコに、シアノピラジン25g(0.238モル)、水加ヒドラジン23.8g(2当量)、酢酸28.6g(2当量)及びメタノール720mLを加え、室温で撹拌した。この混合液を外温50℃にて一晩加熱撹拌した。この反応液を氷冷し、結晶を濾過し、メタノールで洗浄し、減圧下乾燥し、ジヒドロテトラジン粗結晶26.6gを得た。 Production Example 12 Production of 3,6-bis (2-pyrazinyl) -1,2,4,5-tetrazine (1n) Into a 2 L four-necked flask, 25 g (0.238 mol) of cyanopyrazine, hydrazine hydrate 23 .8 g (2 equivalents), 28.6 g of acetic acid (2 equivalents) and 720 mL of methanol were added and stirred at room temperature. The mixture was heated and stirred overnight at an external temperature of 50 ° C. The reaction solution was ice-cooled, the crystals were filtered, washed with methanol, and dried under reduced pressure to obtain 26.6 g of dihydrotetrazine crude crystals.
融点:208-210℃、
1H-NMR(500MHz,CDCl3,δppm):
9.97(s,2H),8.98(s,2H),8.92(d,J =2.1Hz,2H) Half of 13.3 g of dihydrotetrazine crude crystals, 400 mL of tetrahydrofuran and 2.4 L (10 equivalents) of 0.5N hydrochloric acid were added to a 5 L beaker, and the mixture was stirred under ice cooling. 24.6 g (3 equivalents) of sodium nitrite was dissolved in 50 mL of distilled water, added dropwise to the reaction solution over about 0.5 hour, and stirred for 1 hour under ice cooling. Extraction with methylene chloride gave crude crystals by concentration under reduced pressure. The same operation was performed on the remaining half of the dihydrotetrazine crude crystal to obtain 19.1 g of a tetrazine crude crystal. This was dissolved in 960 mL of chloroform, added with 320 mL of n-hexane and filtered, and the filtrate was concentrated under reduced pressure to obtain 11.9 g (red, solid) of the title tetrazine compound (1n).
Melting point: 208-210 ° C
1 H-NMR (500 MHz, CDCl 3 , δ ppm):
9.97 (s, 2H), 8.98 (s, 2H), 8.92 (d, J = 2.1 Hz, 2H)
表1~3に記載の各ゴム成分及びテトラジン化合物をその割合(質量部)で、バンバリーミキサーを用いて混練した。混合物の温度が130~150℃に達した時点から、その温度を維持するように調整しながら約2分間混練し、その後ロールミルで冷却して変性ポリマーを製造した。 Production Examples 13 to 44: Kneading of Modified Polymers Each rubber component and tetrazine compound described in Tables 1 to 3 were kneaded in a proportion (parts by mass) using a Banbury mixer. When the temperature of the mixture reached 130 to 150 ° C., the mixture was kneaded for about 2 minutes while maintaining the temperature, and then cooled with a roll mill to produce a modified polymer.
実施例(表中)において使用する原料を以下に示す。
*1: 溶液重合SBR(S-SBR)、PetroChina Dushanzi Petrochemical Company製、商品名「RC2557S」
*2: 溶液重合SBR(S-SBR)、旭化成ケミカルズ株式会社製、商品名「Tafdene3835」
*3: 溶液重合SBR(S-SBR)、LANXESS社製、商品名「Buna VSL 5025-2」
*4: 溶液重合SBR(S-SBR)、LANXESS社製、商品名「Buna VSL 4526-2」
*5: 溶液重合SBR(S-SBR)、LANXESS社製、商品名「Buna VSL 2538-2」
*6: 末端変性溶液重合SBR(末端変性S-SBR)、日本ゼオン株式会社製、商品名「Nipol NS116R」
*7: 末端変性溶液重合SBR(末端変性S-SBR)、日本ゼオン株式会社製、商品名「Nipol NS616」
*8: 末端変性溶液重合SBR(末端変性S-SBR)、旭化成ケミカルズ株式会社製、商品名「F3420」
*9: 末端変性溶液重合SBR(末端変性S-SBR)、旭化成ケミカルズ株式会社製、商品名「アサプレンY031」
*10: エマルション重合SBR(E-SBR)、Shenhua Chemical Industrial Co., Ltd.製、商品名「SBR1739」
*11: エマルション重合SBR(E-SBR)、日本ゼオン株式会社製、商品名「Nipol 1502」
*12: ブタジエンゴム(BR)、Sinopec Qilu Petrochemical Co., Ltd.製、商品名「BR9000」
*13: 天然ゴム(NR)、GUANGKEN RUBBER社製、商品名「TSR20」
*14: 天然ゴム(NR)、中化国際社製、商品名「RSS3」
*15: イソプレンゴム(IR)、Sterlitamak社製、商品名「IR-1」
*16: イソプレンゴム(IR)、Sterlitamak社製、商品名「IR-2」
*17: イソプレンゴム(IR)、Sterlitamak社製、商品名「SKI-3」
*18: ニトリルゴム(NBR)、日本ゼオン株式会社製、商品名「NBR3350」
*19: クロロプレンゴム(CR)、三井プラスチック貿易有限公司製、商品名「DCR40A」
*20: カーボンブラック、Cabot社製、商品名「N234」
*21: カーボンブラック、Cabot社製、商品名「N330」
*22: カーボンブラック、Cabot社製、商品名「N375」
*23: カーボンブラック、Cabot社製、商品名「N550」
*24: Quechen Silicon Chemical Co., Ltd.製、商品名「HD60MP」
*25: Quechen Silicon Chemical Co., Ltd.製、商品名「HD90MP」
*26: Quechen Silicon Chemical Co., Ltd.製、商品名「HD115MP」
*27: Quechen Silicon Chemical Co., Ltd.製、商品名「HD165MP」
*28: Quechen Silicon Chemical Co., Ltd.製、商品名「HD200MP」
*29: Quechen Silicon Chemical Co., Ltd.製、商品名「HD250MP」
*30: Evonik Industries AG社製、商品名「Si69」
*31: 張家港市国泰華栄化工新材料有限公司製、商品名「SCA-1113」
*32: 張家港市国泰華栄化工新材料有限公司製、商品名「SCA-113」
*33: 張家港市国泰華栄化工新材料有限公司製、商品名「SCA-403」
*34: Kemai Chemical Co., Ltd.製、商品名「6-PPD」
*35: Kemai Chemical Co., Ltd.製、商品名「DPG」
*36: Kemai Chemical Co., Ltd.製、商品名「CBS」
*37: Kemai Chemical Co., Ltd.製、商品名「TMQ」
*38: Kemai Chemical Co., Ltd.製、商品名「DM」
*39: AkzoNobel社製、商品名「DCP」
*40: Kemai Chemical Co., Ltd.製、商品名「TMTD」
*41: Rhein Chemie Rheinau GmbH社製、商品名「Antilux 111」
*42: ステアリン酸、Sichuan Tianyu Grease Chemical Co., Ltd.製
*43: 酸化亜鉛、Dalian Zinc Oxide Co., Ltd.製
*45: 硫黄、Shanghai Jinghai Chemical Co.,Ltd.製
*46: Hansen & Rosenthal社製、商品名「Vivatec 500」
*47: Hansen & Rosenthal社製、商品名「Vivatec 700」
*48: 江蘇宏信化工有限公司製、商品名「DOP」
*49: 浙江黄岩浙東ゴム助剤有限公司製、商品名「MB」
*50: 締展国際貿易有限公司製、商品名「OCTAMINE」
*51: テトラジン化合物(1a):3,6-ビス(3-ピリジル)-1,2,4,5-テトラジン(製造例1で製造した化合物)
*52: テトラジン化合物(1b):3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン、東京化成工業株式会社製
*53: テトラジン化合物(1c):3,6-ビス(4-ピリジル)-1,2,4,5-テトラジン、東京化成工業株式会社製
*54: テトラジン化合物(1d):3,6-ジフェニル-1,2,4,5-テトラジン(製造例2で製造した化合物)
*55: テトラジン化合物(1e):3,6-ジベンジル-1,2,4,5-テトラジン(製造例3で製造した化合物)
*56: テトラジン化合物(1f):3,6-ビス(2-フラニル)-1,2,4,5-テトラジン(製造例4で製造した化合物)
*57: テトラジン化合物(1g):3-メチル-6-(3-ピリジル)-1,2,4,5-テトラジン(製造例5で製造した化合物)
*58: テトラジン化合物(1h):3,6-ビス(3,5-ジメチル-1-ピラゾリル)-1,2,4,5-テトラジン(製造例6で製造した化合物)
*59: テトラジン化合物(1i):3,6-ビス(2-チエニル)-1,2,4,5-テトラジン(製造例7で製造した化合物)
*60: テトラジン化合物(1j):3-メチル-6-(2-ピリジル)-1,2,4,5-テトラジン(製造例8で製造した化合物)
*61: テトラジン化合物(1k):3,6-ビス(4-ヒドロキシフェニル)-1,2,4,5-テトラジン(製造例9で製造した化合物)
*62: テトラジン化合物(1l):3,6-ビス(3-ヒドロキシフェニル)-1,2,4,5-テトラジン(製造例10で製造した化合物)
*63: テトラジン化合物(1m):3,6-ビス(2-ピリミジニル)-1,2,4,5-テトラジン(製造例11で製造した化合物)
*64: テトラジン化合物(1n):3,6-ビス(2-ピラジニル)-1,2,4,5-テトラジン(製造例12で製造した化合物)
*65: 製造例13で製造した変性S-SBR
*66: 製造例14で製造した変性S-SBR
*67: 製造例15で製造した変性S-SBR
*68: 製造例16で製造した変性S-SBR
*69: 製造例17で製造した変性S-SBR
*70: 製造例18で製造した変性S-SBR
*71: 製造例19で製造した変性BR
*72: 製造例20で製造した変性S-SBR・BR
*73: 製造例21で製造した変性S-SBR・BR
*74: 製造例22で製造した変性S-SBR・BR
*75: 製造例23で製造した変性S-SBR・BR
*76: 製造例24で製造した変性S-SBR・BR
*77: 製造例25で製造した変性E-SBR
*78: 製造例26で製造した変性E-SBR
*79: 製造例27で製造した変性S-SBR・E-SBR
*80: 製造例28で製造した変性NR
*81: 製造例29で製造した変性NR
*82: 製造例30で製造した変性NR・BR
*83: 製造例31で製造した変性NR・BR
*84: 製造例32で製造した変性IR
*85: 製造例33で製造した変性NBR
*86: 製造例34で製造した変性S-SBR・BR
*87: 製造例35で製造した変性S-SBR・BR
*88: 製造例36で製造した変性S-SBR・BR
*89: 製造例37で製造した変性S-SBR・BR
*90: 製造例38で製造した変性S-SBR・BR
*91: 製造例39で製造した変性CR
*92: 製造例40で製造した変性S-SBR・BR
*93: 製造例41で製造した変性S-SBR・BR
*94: 製造例42で製造した変性S-SBR・BR
*95: 製造例43で製造した変性S-SBR・BR
*96: 製造例44で製造した変性S-SBR・BR [Explanation of symbols in the table]
The raw materials used in the examples (in the table) are shown below.
* 1: Solution polymerization SBR (S-SBR), manufactured by PetroChina Dushanzi Petrochemical Company, trade name “RC2557S”
* 2: Solution polymerization SBR (S-SBR), manufactured by Asahi Kasei Chemicals Corporation, trade name “Tafdene 3835”
* 3: Solution polymerization SBR (S-SBR), manufactured by LANXESS, trade name “Buna VSL 5025-2”
* 4: Solution polymerization SBR (S-SBR), manufactured by LANXESS, trade name “Buna VSL 4526-2”
* 5: Solution polymerization SBR (S-SBR), manufactured by LANXESS, trade name “Buna VSL 2538-2”
* 6: Terminal-modified solution polymerization SBR (terminal-modified S-SBR), manufactured by Nippon Zeon Co., Ltd., trade name “Nipol NS116R”
* 7: Terminal modified solution polymerization SBR (terminal modified S-SBR), manufactured by Nippon Zeon Co., Ltd., trade name “Nipol NS616”
* 8: Terminal modified solution polymerization SBR (terminal modified S-SBR), manufactured by Asahi Kasei Chemicals Corporation, trade name “F3420”
* 9: Terminal-modified solution polymerization SBR (terminal-modified S-SBR), manufactured by Asahi Kasei Chemicals Corporation, trade name “ASAPREN Y031”
* 10: Emulsion polymerization SBR (E-SBR), manufactured by Shenhua Chemical Industrial Co., Ltd., trade name “SBR1739”
* 11: Emulsion polymerization SBR (E-SBR), manufactured by Nippon Zeon Co., Ltd., trade name “Nipol 1502”
* 12: Butadiene rubber (BR), manufactured by Sinopec Qilu Petrochemical Co., Ltd., trade name “BR9000”
* 13: Natural rubber (NR), manufactured by GUANGKEN RUBBER, trade name “TSR20”
* 14: Natural rubber (NR), manufactured by Chuka Kokusai Co., Ltd., trade name “RSS3”
* 15: Isoprene rubber (IR), manufactured by Sterlitamak, trade name “IR-1”
* 16: Isoprene rubber (IR), manufactured by Sterlitamak, trade name “IR-2”
* 17: Isoprene rubber (IR), manufactured by Sterlitamak, trade name “SKI-3”
* 18: Nitrile rubber (NBR), manufactured by Nippon Zeon Co., Ltd., trade name “NBR3350”
* 19: Chloroprene rubber (CR), manufactured by Mitsui Plastics Trading Co., Ltd., trade name “DCR40A”
* 20: Carbon black, manufactured by Cabot, trade name “N234”
* 21: Carbon black, manufactured by Cabot, trade name “N330”
* 22: Carbon black, manufactured by Cabot, trade name “N375”
* 23: Carbon black, manufactured by Cabot, trade name “N550”
* 24: Product name “HD60MP” manufactured by Quechen Silicon Chemical Co., Ltd.
* 25: Product name “HD90MP” manufactured by Quechen Silicon Chemical Co., Ltd.
* 26: Product name “HD115MP” manufactured by Quechen Silicon Chemical Co., Ltd.
* 27: Product name “HD165MP”, manufactured by Quechen Silicon Chemical Co., Ltd.
* 28: Product name “HD200MP” manufactured by Quechen Silicon Chemical Co., Ltd.
* 29: Product name “HD250MP”, manufactured by Quechen Silicon Chemical Co., Ltd.
* 30: Product name “Si69” manufactured by Evonik Industries AG
* 31: Zhangjiagang City Taitai Huahua Chemical New Materials Co., Ltd., trade name “SCA-1113”
* 32: Zhangjiagang City National Taihua Huakae Chemical New Materials Co., Ltd., trade name “SCA-113”
* 33: Product name “SCA-403” manufactured by Zhangjiagang City National Taihua Huakae Chemical New Materials Co., Ltd.
* 34: Product name “6-PPD” manufactured by Kemai Chemical Co., Ltd.
* 35: Product name “DPG” manufactured by Kemai Chemical Co., Ltd.
* 36: Product name “CBS”, manufactured by Kemai Chemical Co., Ltd.
* 37: Product name “TMQ” manufactured by Kemai Chemical Co., Ltd.
* 38: Product name “DM” manufactured by Kemai Chemical Co., Ltd.
* 39: Product name “DCP” manufactured by AkzoNobel
* 40: Product name “TMTD”, manufactured by Kemai Chemical Co., Ltd.
* 41: Rhein Chemie Rheinau GmbH, trade name “Antilux 111”
* 42: Stearic acid, manufactured by Sichuan Tianyu Grease Chemical Co., Ltd. * 43: Zinc oxide, manufactured by Dalian Zinc Oxide Co., Ltd.
* 45: Sulfur, manufactured by Shanghai Jinghai Chemical Co., Ltd. * 46: Hansen & Rosenthal, trade name “Vivatec 500”
* 47: Product name “Vivatec 700” manufactured by Hansen & Rosenthal
* 48: Product name “DOP” manufactured by Hironobu Jiangsu Chemical Co., Ltd.
* 49: Zhejiang Huangyan Zhedong Rubber Auxiliary Co., Ltd., trade name “MB”
* 50: Trade name “OCCAMINE”, manufactured by Taikan International Trading Co., Ltd.
* 51: Tetrazine compound (1a): 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine (compound produced in Production Example 1)
* 52: Tetrazine compound (1b): 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, manufactured by Tokyo Chemical Industry Co., Ltd. * 53: Tetrazine compound (1c): 3,6-bis (4-Pyridyl) -1,2,4,5-tetrazine, manufactured by Tokyo Chemical Industry Co., Ltd. * 54: Tetrazine compound (1d): 3,6-diphenyl-1,2,4,5-tetrazine (Production Example 2) Compound produced in
* 55: Tetrazine compound (1e): 3,6-dibenzyl-1,2,4,5-tetrazine (compound produced in Production Example 3)
* 56: Tetrazine compound (1f): 3,6-bis (2-furanyl) -1,2,4,5-tetrazine (compound produced in Production Example 4)
* 57: Tetrazine compound (1 g): 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine (compound produced in Production Example 5)
* 58: Tetrazine compound (1h): 3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine (compound produced in Production Example 6)
* 59: Tetrazine compound (1i): 3,6-bis (2-thienyl) -1,2,4,5-tetrazine (compound produced in Production Example 7)
* 60: Tetrazine compound (1j): 3-methyl-6- (2-pyridyl) -1,2,4,5-tetrazine (compound produced in Production Example 8)
* 61: Tetrazine compound (1k): 3,6-bis (4-hydroxyphenyl) -1,2,4,5-tetrazine (compound produced in Production Example 9)
* 62: Tetrazine compound (1l): 3,6-bis (3-hydroxyphenyl) -1,2,4,5-tetrazine (compound produced in Production Example 10)
* 63: Tetrazine compound (1m): 3,6-bis (2-pyrimidinyl) -1,2,4,5-tetrazine (compound produced in Production Example 11)
* 64: Tetrazine compound (1n): 3,6-bis (2-pyrazinyl) -1,2,4,5-tetrazine (compound produced in Production Example 12)
* 65: Modified S-SBR produced in Production Example 13
* 66: Modified S-SBR produced in Production Example 14
* 67: Modified S-SBR produced in Production Example 15
* 68: Modified S-SBR produced in Production Example 16
* 69: Modified S-SBR produced in Production Example 17
* 70: Modified S-SBR produced in Production Example 18
* 71: Modified BR produced in Production Example 19
* 72: Modified S-SBR / BR manufactured in Production Example 20
* 73: Modified S-SBR / BR manufactured in Production Example 21
* 74: Modified S-SBR / BR manufactured in Production Example 22
* 75: Modified S-SBR / BR manufactured in Production Example 23
* 76: Modified S-SBR / BR manufactured in Production Example 24
* 77: Modified E-SBR produced in Production Example 25
* 78: Modified E-SBR produced in Production Example 26
* 79: Modified S-SBR / E-SBR manufactured in Production Example 27
* 80: Modified NR produced in Production Example 28
* 81: Modified NR produced in Production Example 29
* 82: Modified NR · BR produced in Production Example 30
* 83: Modified NR · BR produced in Production Example 31
* 84: Modified IR produced in Production Example 32
* 85: Modified NBR produced in Production Example 33
* 86: Modified S-SBR / BR manufactured in Production Example 34
* 87: Modified S-SBR / BR manufactured in Production Example 35
* 88: Modified S-SBR / BR manufactured in Production Example 36
* 89: Modified S-SBR / BR manufactured in Production Example 37
* 90: Modified S-SBR / BR manufactured in Production Example 38
* 91: Modified CR produced in Production Example 39
* 92: Modified S-SBR / BR manufactured in Production Example 40
* 93: Modified S-SBR / BR manufactured in Production Example 41
* 94: Modified S-SBR / BR manufactured in Production Example 42
* 95: Modified S-SBR / BR manufactured in Production Example 43
* 96: Modified S-SBR / BR manufactured in Production Example 44
(1)S-SBR*2(100質量部)及びテトラジン化合物(1b)(5質量部)をバンバリーミキサーで混練した。混合物の温度が130~150℃に達した時点から、その温度を維持するよう調整しながら約2分間混練し、その後ロールミルで冷却して変性ポリマー(変性S-SBR)を製造した。 Production Example 45 Production of Tetrazine Modified Polymer and Confirmation of Structure (1) S-SBR * 2 (100 parts by mass) and tetrazine compound (1b) (5 parts by mass) were kneaded with a Banbury mixer. When the temperature of the mixture reached 130 to 150 ° C., the mixture was kneaded for about 2 minutes while maintaining the temperature, and then cooled with a roll mill to produce a modified polymer (modified S-SBR).
下記表4~13の工程(A)に記載の各成分をその割合(質量部)で混合し、バンバリーミキサーで混合物の最高温度が160℃になるように回転数を調整しながら5分間混練した。混合物の温度が80℃以下になるまで養生させた後、表4~11の工程(B)に記載の各成分をその割合(質量部)で投入し、混合物の最高温度が110℃以下になるよう調整しながら混練して、ゴム組成物を製造した。 Examples 1 to 129
The components described in the steps (A) of Tables 4 to 13 below were mixed in the proportions (parts by mass), and kneaded for 5 minutes with a Banbury mixer while adjusting the rotation speed so that the maximum temperature of the mixture was 160 ° C. . After curing until the temperature of the mixture reaches 80 ° C. or less, each component described in Steps (B) of Tables 4 to 11 is added in the proportion (part by mass), and the maximum temperature of the mixture becomes 110 ° C. or less. The rubber composition was manufactured by kneading while adjusting as described above.
下記表14の工程(A-1)に記載の各成分をその割合(質量部)で混合し、バンバリーミキサーで混合物の温度が表14に記載の温度(混合物温度)を保つように回転数を調整しながら、表14に記載する時間(混練時間)混練した後、工程(A-2)に記載の各成分をその割合で投入し、混合物の温度が160℃になるよう調整しながら4分間混練した。混合物の温度が80℃以下になるまで養生させた後、表14の工程(B)に記載の各成分をその割合で加えて、バンバリーミキサーで最高温度が110℃以下になるように回転数を調整しながら1分間混練して、ゴム組成物を製造した。 Examples 130-133
The components described in the step (A-1) in Table 14 below are mixed in the ratio (parts by mass), and the number of revolutions is adjusted so that the temperature of the mixture maintains the temperature described in Table 14 (mixture temperature) with a Banbury mixer. While kneading, the components shown in Table 14 (kneading time) were kneaded, and then each component described in step (A-2) was added at the ratio, and the temperature of the mixture was adjusted to 160 ° C. for 4 minutes. Kneaded. After curing until the temperature of the mixture reaches 80 ° C. or less, add each component described in step (B) of Table 14 at that ratio, and adjust the number of rotations so that the maximum temperature is 110 ° C. or less with a Banbury mixer. The rubber composition was manufactured by kneading for 1 minute while adjusting.
下記実施例1~133のゴム組成物について、粘弾性測定装置(Metravib社製)を使用し、温度40℃、動歪5%、周波数15Hzでtanδを測定した。比較するために、テトラジン化合物を添加しない以外は、各実施例と同じ配合内容及び同じ製法でゴム組成物(リファレンス)をそれぞれ作製し、そのtanδの逆数をそれぞれ100とした。下記式に基づいて、低発熱性指数を算出した。なお、低発熱性指数の値が大きい程、低発熱性であり、ヒステリシスロスが小さいことを示す。また、それぞれのリファレンスの加硫ゴム組成物の低発熱性は100とする。
式:低発熱性指数={(テトラジン化合物(1)を添加していないゴム組成物のtanδ)/(本発明のゴム組成物のtanδ)}×100 Low exothermic property (tan δ index) test The rubber compositions of Examples 1 to 133 below were measured for tan δ at a temperature of 40 ° C, a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metravib). For comparison, a rubber composition (reference) was prepared with the same blending contents and the same manufacturing method as in each example except that no tetrazine compound was added, and the reciprocal of tan δ was set to 100, respectively. Based on the following formula, a low exothermic index was calculated. In addition, it shows that it is low exothermic property and a hysteresis loss is so small that the value of a low exothermic index is large. The low exothermic property of each reference vulcanized rubber composition is 100.
Formula: Low exothermic index = {(tan δ of rubber composition not containing tetrazine compound (1)) / (tan δ of rubber composition of the present invention)} × 100
Claims (12)
- ゴム成分に低発熱性を付与するための添加剤であって、
下記一般式(1):
で表されるテトラジン化合物又はその塩を含む、添加剤。 An additive for imparting low heat build-up to the rubber component,
The following general formula (1):
The additive containing the tetrazine compound or its salt represented by these. - X1及びX2が、複素環基である請求項1に記載の添加剤。 The additive according to claim 1, wherein X 1 and X 2 are heterocyclic groups.
- ゴム成分が、ジエン系ゴムである請求項1又は2に記載の添加剤。 The additive according to claim 1 or 2, wherein the rubber component is a diene rubber.
- ゴム成分、及び請求項1~3のいずれか一項に記載の添加剤を含むゴム混合物を用いて作製された変性ポリマー。 A modified polymer produced by using a rubber mixture comprising a rubber component and the additive according to any one of claims 1 to 3.
- ゴム成分が、ジエン系ゴムである請求項4に記載の変性ポリマー。 The modified polymer according to claim 4, wherein the rubber component is a diene rubber.
- ゴム成分、請求項1~3のいずれか一項に記載の添加剤、並びに無機充填材及び/又はカーボンブラックを含むゴム組成物。 A rubber composition comprising a rubber component, the additive according to any one of claims 1 to 3, and an inorganic filler and / or carbon black.
- 請求項4又は5に記載の変性ポリマー、並びに無機充填材及び/又はカーボンブラックを含むゴム組成物。 A rubber composition comprising the modified polymer according to claim 4, and an inorganic filler and / or carbon black.
- ゴム成分が、ジエン系ゴムである請求項6に記載のゴム組成物。 The rubber composition according to claim 6, wherein the rubber component is a diene rubber.
- トレッド部、サイドウォール部、ビードエリア部、ベルト部、カーカス部及びショルダー部から選ばれる少なくとも一つの部材に用いられる、請求項6~8のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 6 to 8, which is used for at least one member selected from a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion and a shoulder portion.
- 請求項6~8のいずれか一項に記載のゴム組成物を用いて作製されたタイヤ。 A tire produced using the rubber composition according to any one of claims 6 to 8.
- ゴム成分、請求項1~3のいずれか一項に記載の添加剤、及び無機充填材及び/又はカーボンブラックを含む原料成分を混合する工程(A)、並びに
工程(A)で得られる混合物、及び加硫剤を混合する工程(B)を含む、ゴム組成物の製造方法。 A step (A) of mixing a rubber component, an additive according to any one of claims 1 to 3 and a raw material component containing an inorganic filler and / or carbon black, and a mixture obtained in step (A); And a method for producing a rubber composition, comprising a step (B) of mixing a vulcanizing agent. - 工程(A)が、ゴム成分、及び請求項1~3のいずれか一項に記載の添加剤を混合する工程(A-1)、並びに
工程(A-1)で得られた混合物、及び無機充填材及び/又はカーボンブラックを混合する工程(A-2)である、請求項11に記載の製造方法。 Step (A) is a step (A-1) of mixing a rubber component and the additive according to any one of claims 1 to 3, and a mixture obtained in step (A-1), and an inorganic material. The production method according to claim 11, which is a step (A-2) of mixing a filler and / or carbon black.
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US15/763,933 US20180273723A1 (en) | 2015-09-30 | 2016-09-30 | Additive for imparting low heat build-up to rubber component |
CN201680054491.5A CN108026332B (en) | 2015-09-30 | 2016-09-30 | Additive for imparting low heat build-up to rubber component |
KR1020187008150A KR102592174B1 (en) | 2015-09-30 | 2016-09-30 | Additives to provide low heat generation properties to rubber components |
BR112018005307-4A BR112018005307B1 (en) | 2015-09-30 | 2016-09-30 | RUBBER COMPOSITION, USES, TIRE, TREADMILL, SIDE WALL, CORD AREA, BELT, CARCASS AND SHOULDER PORTION |
EP16851927.0A EP3357961B1 (en) | 2015-09-30 | 2016-09-30 | Additive for imparting low heat build-up to rubber component |
JP2016572604A JP6148799B1 (en) | 2015-09-30 | 2016-09-30 | Additive for imparting low heat build-up to rubber components |
US16/812,124 US20200231782A1 (en) | 2015-09-30 | 2020-03-06 | Additive for imparting low heat build-up to rubber component |
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US16/812,124 Division US20200231782A1 (en) | 2015-09-30 | 2020-03-06 | Additive for imparting low heat build-up to rubber component |
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US20210388188A1 (en) * | 2020-06-11 | 2021-12-16 | The Goodyear Tire & Rubber Company | Pneumatic tire and rubber composition including tetrazine modified elastomer and zinc complex compound |
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Also Published As
Publication number | Publication date |
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US20200231782A1 (en) | 2020-07-23 |
EP3357961A1 (en) | 2018-08-08 |
JPWO2017057758A1 (en) | 2017-10-05 |
CN108026332B (en) | 2020-12-01 |
BR112018005307A2 (en) | 2018-10-09 |
JP2017179376A (en) | 2017-10-05 |
JP6148799B1 (en) | 2017-06-14 |
KR20180059776A (en) | 2018-06-05 |
CN108026332A (en) | 2018-05-11 |
JP6859184B2 (en) | 2021-04-14 |
EP3357961A4 (en) | 2019-04-17 |
EP3357961B1 (en) | 2022-01-05 |
KR102592174B1 (en) | 2023-10-19 |
BR112018005307B1 (en) | 2022-08-30 |
CN112111090A (en) | 2020-12-22 |
US20180273723A1 (en) | 2018-09-27 |
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